The milliner Stephen Jones has spent the past two years scouring the world for the rarest and most beautiful headgear ever created. He tells Lena Corner about his new exhibition at the V&A, and tips a hat to his 20 all-time favourite designs

For the past two years the milliner Stephen Jones has been a man on a mission. Ever since London's V&A asked him to curate its first ever show devoted entirely to hats, he has been crossing continents, cutting deals with owners and rifling through long-forgotten boxes to create the ultimate collection.

He started in the attic of the V&A. "I must have gone through 4,000 hats," he says. "One of my best finds was an incredible Tudor knitted beret which was squashed into a big mahogany drawer that hadn't been opened in 20 years."

Elsewhere he has discovered such delights as a miniature Stetson, just two inches high, from a private collector in America, and Dame Margot Fonteyn's Dior cloche hat, which he unearthed in Bath. But of all the hats he found, his favourite came from a random tip-off via Mick Jagger.

"I was doing a hat fitting with him and telling him all about the exhibition when his girlfriend, the designer L'Wren Scott, happened to mention she thought she knew where all the hats from My Fair Lady were. Well, for a milliner, those hats are the holy grail. That film was pure hat porn."

Following Scott's instructions, Jones eventually found himself in a small store cupboard belonging to Warner Brothers in Los Angeles. "It was stacked with huge boxes and there they were in front of me – all the hats from the film. It was a truly unbelievable moment."

It's clear the V&A picked the right man for the job, and Jones, who has been in the business for more than 30 years, has relished the task of millinery super-sleuth. "For me, hats aren't an accessory, they are the raison d'être of an outfit. They don't just make you look pretty, they take you somewhere else; they can change, destroy and create emotions." In the fashion world he is widely acknowledged to have an encyclopaedic knowledge of his subject.

But Jones hasn't always been a man on such a mission. Born on the Wirral in 1957, he was, he says, a late starter. "I was never one of those people making hats with their mother at the age of two," he says. "It all happened quite organically." In the mid-1970s he enrolled at St Martins on the women's fashion course ."I was the token male," he says, "but sadly my work in the first year didn't progress as everyone had hoped." Then a chance meeting with two women from the millinery department changed everything. Jones went home, and over the space of one weekend, whipped up his first creation, "It was a pillbox hat made out of turquoise crepe de Chine with silver piping. It was trimmed with a blue plastic iris sprayed silver, which my mother had got free with her petrol in the 1960s." For his efforts, Jones was allowed to transfer to the millinery course.

He graduated from St Martins on to a London scene in a state of flux. Punk was losing its momentum and in its place a new centre of creativity sprang up around the legendary Blitz nightclub started by Steve Strange and frequented by the likes of John Galliano and Leigh Bowery. "I started making hats for the club kids," he says, "for people such as Boy George and Spandau Ballet. Then they started to become famous and it kind of all began there."

Princess Diana became a customer and Jones has since extended his roll call of clients to include Gwen Stefani, Kylie, Beyoncé and the Rolling Stones, among others. It's mainly thanks to Jones' work that, since the early-1980s, London has become recognised as the global centre for millinery.

These days, as well as working with Galliano for Dior, Jones continues to make hats – whimsical, spectacular and absurd – from his shop in Covent Garden. His drive to create is as strong as ever. Show him a picture of Marlene Dietrich in a black felt beret and he's out of his seat. "Look at that," he cries. "That is my challenge: to make a hat as good as a beret – the most simple, beautiful, practical headpiece there is. It will bug me until the day I'm six feet under." Who better, then, than Stephen Jones to compile a list for the Independent on Sunday of the top 20 hats the world has ever seen. '

Hats: an Anthology by Stephen Jones is at the V&A (0844 209 1770, from Saturday to 31 May

Stephen Jones: My 20 favourite hats

1. Marlene Dietrich's Spanish comb

The great thing about this hat is the placement on Dietrich's head. One thing I learnt from working with John Galliano is that hats are all about making a frame for the face. And this is one of the best frames I've seen. The harmony between hair, make-up and clothing is perfect, yet somehow you are still drawn to her face.

2. Simone Mirman's Langoustine Fantasia

Simone Mirman was the Queen's milliner in the 1960s. I just love the fact that this hat is based on langoustine. Philip Treacy summed it up when he said, "Wearing a hat is like having a party on your head." That's exactly what this is. It's eye candy, it means nothing, it's just fun.

3. Queen Mother's tulle

Cecil Beaton took this photograph of the Queen Mother in 1939 just before the outbreak of war, so it was deemed too extravagant to publish. The hat is now a dirty chocolate brown, because it's so full of dust, but it's a truly magical image.

4. Straw policeman's helmets

The navy-blue policeman's hat is such a great British icon and I just love the fact that someone has thought to remake it using straw. The only two places where they wore them were Luton, which is the centre of the straw-hat business in the UK, and Singapore.

5. Carmen Miranda's turban

Turbans are wonderfully basic – take a piece of fabric and wrap it round your head. Carmen Miranda started out as milliner, so when she said I want a pompom here or piece of fruit there, she knew exactly what she was doing.

6. Billie Holliday with gardenias

What is more beautiful than fresh flowers pinned to a woman's hair? Billie Holiday loved gardenias. The chalky-white colour looked so beautiful against her skin and the amazing scent went everywhere with her. They came from South America and were fabulously expensive but she got new ones every day. They were her luxury.

7. Stephen Jones' Rose Royce

This is the only one of my own designs I've chosen. It's basically a top hat and everybody – man, woman or animal – looks sexy in a top hat. I was trying to find a new way to represent flowers and ended up with this – a rolled-up piece of satin. It pulls together so many things that I love about millinery – it's simple, lyrical and easygoing.

8. King Tut's crown, by Dior

This shape has all sorts of symbolic meanings about power and religion but at the same time it is simply one of the most pure and beautiful architectural forms. There is something very beautiful about the line it creates. It elongates the neck and traces a gorgeous path through the chin and out through the crown of the head to the heavens.

9. Mrs Gertrude Shilling's 1973 Europe hat

This is Mrs Shilling, mother of the milliner David Shilling. She was a wonderful eccentric and every year her hats were the talking point of Ascot. Here she is in her EEC hat (the designs were often vaguely topical). She always had to get dressed around the corner because she couldn't fit into the car, and one year her hat was so big that she couldn't even get through the gates.

10. Elizabeth Taylor's headdress from Boom

Elizabeth Taylor wore this in a film called Boom. I love it because I'm sure it's the work of some crazed old set designer and it's all stuck together with a hot glue gun. There's some really cheap white marguerites and fake coral which looks as though it is made from cigarettes. But it just goes to prove that you can make a million-dollar hat out of dime-store material.

11. Dior bicorn, 1949

The great thing about Dior is that even though he did incredibly extravagant work, when you see the originals they are very disciplined and this hat is much smaller than it looks. It's a shape I've revisited quite a lot because, if you have width to the side of your face, it gives a gorgeous jawline and cheekbones.

12. 1940s day hat

This was made in the 1940s, back when everybody wore hats, by an American company called Braggard. I love the fact that it's a real expression of frivolity yet it's made in green and brown, not fuchsia pink. It would have been worn by a woman in a tweed suit on her way to lunch.

13. Seventeenth-century leather bonnet

This is the one I found in the drawer at the V&A. It's a boiled leather cap with the most simple stitching. The leather is about 5mm thick and absolutely rock-hard. This is something I would have loved to have made for Comme des Garçons but there it was, done... 400 years ago.

14. Schiaparelli shoe hat

I've been inspired throughout my career by this 1940s hat by Schiaparelli, which just happens to look like a shoe. Surrealism and millinery are a perfect match. There are only three in existence, so they are incredibly expensive. The V&A has purchased one for the show, so I am very excited.

15. Marlene Dietrich's Schiaparelli beret

What could be more elegant than a black beret? It's the T-shirt of hats. It can be worn in so many different ways then rolled up and put in your pocket. There's something universal about it – adults and children wear them and so do the rich and poor. When we contacted the Film Museum in Berlin to ask for one of Dietrich's berets they said, "Yes, we have 85 of them. Do you want Schiaparelli or Kangol?"

16. Queen Elizabeth II's headscarf

I do love a headscarf and the Queen has worn one all her life; even while driving a tank. It's a fabulous design as it's a simple square of fabric, practical, disposable, yet individual. In the 1950s every housewife wore one.

17. Darth Vader

Exactly the same shape as a Japanese samurai helmet, denoting power and strength. I went to see Star Wars when it came out in 1977, my second year of college, the second year of punk. It was an exciting time for me.

18. Dancer's hat from My Fair Lady by Cecil Beaton

This is the hat from My Fair Lady that we discovered flattened in a cardboard box in a costume cupboard in LA. It is one of my favourite hats of all time. It's a velvet, asymmetric pointed hat, which is quite a simple thing in itself, yet its proportions are very extravagant and beautiful. I'm going to restore it myself.

19. Eighteenth-century straw hat with straw flowers

This is so British and so pretty. It's also well preserved – whoever dyed those flowers certainly knew what they were doing. Hats can be wild and wacky, formed out of plastic and flashing lights, but sometimes it's quite nice to make things which are familiar and reassuring.

20. An ibex's horns

We thought Mrs Shilling was bonkers, but this is even more so. This is a fabulous, extraordinary headdress. The symmetry is perfect. I've tried many times to make the perfect set of horns but it has always eluded me.