President Jacob Zuma announced his resignation with immediate effect on Wednesday night.
"Even though I disagree with the decision ... I have always been a disciplined member of my organisation," he said.
Zuma was speaking from the Union Buildings in Pretoria on Wednesday night.
Zuma's statement comes after the ANC gave him an ultimatum to resign or be recalled in a letter delivered by the party's secretary general Ace Magashule on Tuesday.
On Wednesday the ANC announced that their MPs would vote with opposition parties in support of a motion of no confidence against Zuma and that the Speaker of Parliament had agreed to move the motion, which was originally scheduled to be debated next week, forward to Thursday.
The ANC gave Zuma until midnight on Wednesday to respond to the recall letter, otherwise the debate on the motion of no confidence will commence at 2pm on Thursday as agreed to by all political parties.
A defiant Zuma earlier on Wednesday spoke out in an interview with the SABC, saying he had done nothing wrong and was never told the reasons for his recall.
He stated that he disagreed with the decision of the ANC to recall him, and warned that it would plunge the country into a “crisis”.
Zuma said he had made it clear to the party's national officials that he was not willing to leave the Union Buildings without being told what wrong he had committed. He said he felt victimised.