Martin and Judith Miller, who now live apart, made a fortune from sales of the guide, but now face personal losses of more than pounds 2m.
Mrs Miller is the co-presenter with Ross Benson of the Channel 4 antiques programme, For Love or Money.
The couple owned Chilston Park Hotel in Sandway near Maidstone, Kent, a 17th century hotel known for attracting the rich and famous. The Grade I listed building was under their management for 10 years.
They sold the property in December last year for pounds 2m while trading under the name of Chilston Park Hotel - a name they changed recently to Waylen 1996.
But at the end of January this year the receivers Coopers & Lybrand were called in by Lloyds Bank to sort out mounting debts.
In a letter sent to creditors it was revealed that the couple's company owed pounds 486,000 to the bank, pounds 68,000 to Customs and Excise and pounds 28,000 to the Inland Revenue. More than pounds 2.3m is said to be directors' loans.
Businesses across the country are thought to be owed around pounds 92,000 and receivers say that they are unlikely to receive the cash back.
The debt also includes those incurred while the couple were trading in partnership as MJM Property Developments.
A spokesman for Coopers & Lybrand, based in Maidstone, said: "Mr and Mrs Miller are a charming couple and I am not prepared to go into the amounts owed other than to say it is a rather large sum.
"There is a meeting with the creditors next week [at Bearsted, near Maidstone] and it is only right that we wait until then before going any deeper into the situation."
Mr Miller, who now lives in south-west London, was unavailable for comment yesterday.