South African Finance Minister Trevor Manuel and nine other cabinet members are resigning along with President Thabo Mbeki.
The BBC's Peter Biles says the resignations are a major blow to the ANC government - especially the loss of the respected Mr Manuel.
The ANC is divided between supporters of Mr Mbeki and ANC leader Jacob Zuma.
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Mr Mbeki is to leave office on Thursday after accusations that he interfered in the prosecution of Mr Zuma on corruption charges.
As ANC leader, Mr Zuma is favourite to become South Africa's next president.
Mr Manuel is seen as instrumental in South Africa's recent economic stability.
Our correspondent says his departure could trigger political and financial uncertainty in South Africa.
Mr Mbeki on Saturday accepted a decision by the ANC to recall him as president.
Correspondents say the ANC's hopes of managing a stable transition have now been thrown out of the window.
A close ally of Mr Zuma - ANC deputy leader Kgalema Motlanthe - is to replace Mr Mbeki as president until next year's elections, the ANC says.
(BBC)
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