Caine and his wife Shakira are selling their other home in Hollywood to spend more time in Britain. The art collection has decorated their American base for some years.
The collection, which will be auctioned by Sotheby's in London this autumn, is made up of dozens of art deco and art nouveau objects and a pen and ink drawing by Henry Moore, in addition to the paintings. Once the couple had shipped the artwork back from the US, it became clear there was not enough room for it to fit alongside pieces the couple already own in Britain.
Caine said yesterday: "I had hoped we might be able to squeeze the two collections together, but there simply isn't the room. I shall be sorry to part with the things we had when we lived in Los Angeles, but I was concerned that the more fragile pieces could get damaged by being crammed in too tightly."
He bought most of the artwork during a brief period of collecting in the late 1960s at a time when art nouveau and art deco were being rediscovered.
A Sotheby's spokesman said: "It is certainly rare for a famous person to sell a collection built up over many years like Michael Caine has done. Part of the appeal of all these works, beyond their intrinsic merit, is the fact that they are fresh to the market after 25 years."
A pen and ink portrait by Picasso of his mistress Dora Maar, signed and dated 16 July 1945, is estimated to sell for up to pounds 15,000. A charcoal pen, ink and pencil drawing entitled Two Figures by Henry Moore from 1943 could fetch up to pounds 6,000. There are also paintings by Paul Nash, Charles Ginner and Henri Gaudier-Brzeska
A signed water colour by Salvador Dali, Trois Personnages Assis, is estimated at between pounds 4,000 and pounds 6,000.The prints include Marc Chagall's Les Amoureux sous l'Arbre, expected to fetch up to pounds 18,000.
Art nouveau and art deco pieces include works by Galle, Daum, Tiffany, Lalique, Mucha and Erte. The vases by Emile Galle are likely to fetch some of the biggest prices. One inscribed with a verse from Baudelaire could sell for up to pounds 20,000, and a large elephant vase could fetch up to pounds 35,000.
Phillipe Garner, head of 20th-century decorative arts at Sotheby's, said: "When I started at Sotheby's, I knew Michael Caine was an enthusiastic collector who was acquiring good examples of art nouveau and art deco. I am delighted, a quarter of a century later, to be asked to sell this delightful collection which might hopefully introduce new collectors to the market."