Pop superstar Madonna will be represented by Fiona Shackleton who acted for Sir Paul McCartney in his £24.3 million split from Heather Mills earlier this year.
Facing her will be Helen Ward, who secured £48 million for Beverley Charman when she split from her insurance magnate husband John in 2006.
Mrs Charman's payout is thought to be the biggest divorce award in English legal history.
A spokesman for film director Ritchie confirmed he had hired Manches, the firm where Lady Ward is a partner, but would not say which lawyer would represent him. Manches refused to comment.
According to the firm's website Lady Ward "specialises in family law, with emphasis on the financial consequences of the breakdown of relationships with particular expertise in cases involving substantial assets, complexity and an international element."
It adds: "Where it is necessary she also deals with cases involving the resolution of disputes relating to the children."
Arrangements for the couple's children are likely to be central to Madonna and Ritchie's divorce.
The singer has a 12-year-old daughter, Lourdes, from a previous relationship. The couple have an eight-year-old son, Rocco, and adopted their younger son, David, three, from Malawi.
The divorce was announced in a joint statement released on Thursday, nearly eight years after the couple's lavish wedding at Skibo castle, Scotland, on December 22, 2000.
The announcement followed months of speculation that the relationship was on the rocks.
Ritchie tried to scotch rumours of a split with a public show of support at his wife's 50th birthday party in August when the couple partied with friends at London nightclub Volstead.
Last month the couple walked arm-in-arm down the red carpet for the world premiere of his latest film RocknRolla in Leicester Square.
Madonna is currently on the US leg of her Sticky and Sweet global tour while Ritchie is shooting his new film, a Sherlock Holmes remake.