Scandal-tainted Zuma said in a 30-minute national television address that he had "come to the decision to resign as president of the republic with immediate effect".
"I have served the people of South Africa to the best of my ability. I am forever grateful that they trusted me with the highest office in the land," he said.
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He complained about the process, saying: "I don't fear exiting political office however I have only asked my party to articulate my transgressions and the reason for its instructions that I vacate office."
Zuma has been at loggerheads with deputy president Cyril Ramaphosa, his expected successor as president and the new head of the ANC.
Parliament could elect Ramaphosa as president as early as Thursday or Friday.
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