Sir Philip and Lady Green appear on a list of the richest couples in the country - although their wealth is said to have fallen by £433 million over the last year.
They were ranked in fifth place in the husbands and wives section of the new edition of the Sunday Times Rich List, to be published on Sunday May 7.
Ernesto and Kirsty Bertarelli top the list of the richest husbands and wives, with wealth put at £11.5 billion.
Those behind the list said the couple's fortune is largely derived from the sale of the family biotech business Serono and the soaring share value in a further pharma business, Santhera.
Charlene de Carvalho-Heineken, the daughter of late Heineken boss Freddy Heineken, and her husband Michel de Carvalho were identified as the second wealthiest couple in the UK with a fortune put at £9.3 billion.
Cumulatively, the 10 richest husbands and wives in the UK have seen their fortune increase by £3.4 billion in the past 12 months, according to the Sunday Times Rich List.
Sir Philip and Lady Green were the only couple on the list whose wealth was said to have decreased over the last year. They have seen their wealth fall by £433 million to £2.787 billion, the Sunday Times Rich List found.
Arcadia boss Sir Philip agreed to pay £363 million to settle the BHS pension scheme in February. The department store chain plunged into administration just over a year ago.
In total, the 10 couples on the list are worth £39.9 billion, according to the findings.
At 160 pages, this year's Sunday Times Rich List - the 29th annual edition to be produced - is the biggest ever. The "definitive guide to wealth" charts the fortunes of the 1,000 richest individuals and families in the British Isles.
Robert Watts, compiler of the Sunday Times Rich List 2017, said: "This year's Sunday Times Rich List will show how the make-up of Britain's richest 1,000 people is changing - with a record number of women and more husband and wife partnerships than before.
"Starting a business with your other half may not appeal to everyone. A bit of pillow talk about balance sheets wouldn't suit all marriages, but there are clearly some couples who are making it work - and very well.
"The growing number of women we're seeing in the Rich List is part of a greater diversity, with more people from ethnic backgrounds and more surprising walks of life, with soft toy makers and dating app developers lining up with private-equity barons and hedge-fund managers."
Here are the top 10 richest husbands and wives according to the Sunday Times Rich List 2017:
1. Ernesto and Kirsty Bertarelli, £11.5 billion, up £1.72 billion
2. Charlene de Carvalho-Heineken and Michel de Carvalho, £9.3 billion, up £150 million
3. Alejandro Santo Domingo and Lady Charlotte Wellesley, £3.862 billion, (new)
4. Francois-Henri Pinault and Salma Hayek, £3.437 billion, up £1.087 billion
5. Sir Philip and Lady Green, £2.787 billion, down £433 million
6. Sir Michael Moritz and Harriet Heyman, £2.629 billion, up £679 million
7. Chris and Sarah Dawson, £1.9 billion, up £150 million
8. Douglas and Dame Mary Perkins, £1.6 billion, up £50 million
9. Poju and Anita Zabludowicz, £1.5 billion, no change
10. Georg and Emily von Opel, £1.416 billion, up £16 million