Laura Ashley boss Khoo Kay Peng and former beauty queen Pauline Chai have already spent £2m disputing which court should rule how the money is split.
Ms Chai says her husband is worth £440m, something Dr Peng denies.
The divorce could be one of England's most expensive after a High Court judge sitting in London said it could be heard in either England or Malaysia.
Earlier in the year a judge described the amounts spent on preliminary legal "skirmishes" as "eye-watering."
Dr Khoo, 75, says the pair's home was in Malaysia and wants to fight his case there, however 67-year-old Ms Chai says they moved to Hertfordshire before separating last year.
Mr Justice Holman said Dr Khoo owned a "chunk" of Laura Ashley and had properties in England and Malaysia worth more than £50m.
He added that Ms Chai, who was crowned Miss Malaysia 1969, could get tens of millions from the divorce.
Despite the judge giving the green light for the divorce to be heard in England, as Ms Chai desires, Dr Khoo has started divorce proceedings in Malaysia with a hearing due there next month.
Mr Justice Bodey, sitting in the Family Division of the High Court, said he was "urging the parties with all the strength I can muster" to redouble their efforts "to reach a financial accommodation" and avoid the nightmare of a legal battle in two jurisdictions.
He added that there was "enough in the kitty" and they would be hard pushed to spend it all in their own lifetimes "even if they wanted to."
After the ruling, Ms Chai, said: "I am proud to be one of the beneficiaries of one of the greatest gifts that the English have given to the world: the rule of law."
The estranged pair married in 1970 and have five children together.