Between them the couple are worth more than £300million, but rather than the cash, children Lourdes, Rocco and David are said to be the main area of contention.
The singer is believed to want to raise her three children in New York. But Guy has set his sights on them growing up in London and Wiltshire and is upset about them being on the other side of the Atlantic.
A source said: 'Madonna wants them to be brought up in the cosmopolitan environment of New York.
Fight for their kids: Madonna and Guy, here with children Lourdes and Rocco, are said to be facing up to a bitter custody battle
'Guy wants them to continue growing up in London and Wiltshire, being privately educated in Britain.
'This has been the major stumbling block as to why their lawyers have not been able to negotiate an out-of-court settlement.'
The source said that Ritchie's parents, John Ritchie and Amber, Ladly Leighton - who are now divorced - are also distraught at the idea of Madonna having the children on the other side of the Atlantic.
'Amber, who was adopted herself, is furious that Guy and Madonna have not been able to settle their differences for the sake of the children,' the source added.
'Guy is really upset that his parents may be prevented from seeing Rocco. Rocco is Guy's beloved little boy.
The show must go on: After announcing her divorce, Madonna returned to doing what she does best after announcing the split - performing on stage in Boston
The signs that the divorce was heading towards acrimony couldn't have been clearer yesterday as the singer made a very thinly-veiled attack on Guy Ritchie for being 'emotionally retarded' live on stage.
Performing in Boston a few hours after their break-up was announced, she told the audience: 'This song is for the emotionally retarded. Maybe you know some people who fall into that category. I know I do.'
The song she then performed was Miles Away, inspired, she once said, by her often long-distance relationship with Ritchie.
She also opened the show, which took place just hours after her spokesperson confirmed the split, with her track I'm Not Sorry, telling the 20,000-strong crowd: 'That's right, I'm not sorry.'
'They do everything together. He adores him. He wants him to be a Londoner.
'The idea that he will be across the Atlantic from him most of the time is really tearing him apart.
'Guy is really frustrated that Madonna is building a legal case on her being this earth mother-style primary carer who looks after the children most of the time.'
Broken man: Guy Ritchie cut a folorn figure on the set of Sherlock Holmes in London yesterday
'They have both requested that the media maintain respect for their family at this difficult time. A final settlement has not been agreed upon yet.'
Madonna had been sending Guy messages their marriage was over months ago when she began moving some of their art collection, including a Dali and portrait of Napoleon Bonaparte by Jacques-Louis David from their London home to their New York residence.
The singer is understood to have already offered Ritchie their country estate Ashcombe House, which is worth some £12million, plus a lump sum of as little as £15million.
Legal experts estimate that he could fight for up to £75million, comprising half the estimated £80million they have earned between them over their ten-year relationship, a further regular maintenance payout and properties.
Such an amount would dwarf Britain's largest divorce settlement so far of £48million, paid by insurance magnate John Charman to wife Beverley in 2006.
The gig at the city's Banknorth Garden was the 23rd concert of the Sticky & Sweet World Tour, which started in Cardiff in August and is expected to end in December.
Madonna cryptically announced to a New York concert audience on October 6: 'In exactly 29 moves, the Queen will dump the King.' She then had 29 more dates on her U.S. tour.
But in the light of the announcement, it seems she simply could not wait that long.
The couple are now lining up for what could become the costliest divorce in British legal history.
Sombre: Madonna returning to her New York apartment on Tuesday night hours before the announcement
Madonna, who has an estimated personal fortune of £275million, has already lined up a fearsome legal team including the so-called 'Steel Magnolia' Fiona Shackleton and Nicholas Mostyn QC, the lawyers Sir Paul McCartney employed for his vicious two-year divorce battle with Heather Mills.
However friends of Ritchie's argue that, after a combative marriage, we can expect a peaceful divorce. Those hoping for a high-profile spat will be disappointed, they say.
In recent months, Madonna has grown close to Lourdes's father Carlos Leon.
Personal trainer Leon has been overseeing renovations on the singer's New York apartment.
He was adamant Madonna and Ritchie's split should not affect Lourdes's 12th birthday on Tuesday.
The Mail has learned that Madonna and Ritchie called time on their marriage after months of arguing over a wide range of issues.
The rows culminated in an almighty fall-out last Friday in which the singer gave her husband an ultimatum to move from London to New York with her. Ritchie, 40, reacted furiously and refused to relocate - sealing their fate.
It was the tipping point in a long battle which has seen them become increasingly alienated, to the point where they were communicating through their PAs.
Cracks in the marriage were apparent in June, when they attended marriage counselling with Kabbalah elders near their home in London. They emerged with a plan they hoped would save their marriage.
Both pledged to reduce their work schedules and not to be apart for more than a week at a time. They also pledged to support one another's interests and when necessary, career choices.
Ritchie had reportedly become increasingly disillusioned with the Kabbalah - a mystical offshoot of Judaism, which Madonna has followed since 1997.
In the end, it was Madonna's plan that the family should move to America which sealed their fate.
One well-placed source said: 'Madonna told him that she had tired of Britain and the British press who had crucified her over the adoption of David Banda.'
By that time, she had already been spending increasing amounts of time in New York - and that brought its own dangers.
There have been rumours of her growing closeness to the U.S. baseball player Alex Rodriguez (A-Rod), and she has been spotted dining with him recently in New York.
'Madonna has a growing closeness with A-Rod. It's nothing sexual, it's what you might call a non-physical affair,' the source said. 'But the point is that Madonna clearly feels A-Rod nourishes her in some way that Guy cannot.'
Perhaps worst of all, the couple have not shared a bed in almost a year, the source claims.
Significantly, the couple are already getting on with their different lives in Britain and America.
Yesterday, while Guy was directing his latest film, about Sherlock Holmes, at a closed studio in Hatfield, Hertfordshire, while Madonna performed a concert in Boston as part of her current world tour.
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