Corzine "voluntarily" quit his posts as MF Global chairman and chief executive, Bloomberg reported.
He will not seek severance pay, a company statement said. He would have been entitled to a $12-million payout, according to the New York Times.
Resignation was a "difficult decision, but one that I believe is best for the firm and its stakeholders," Corzine said.
More from GlobalPost: MF Global files for Chapter 11 bankruptcy
It comes four days after MF Global filed the 8th-largest bankruptcy in US history.
Investigators including the Securities and Exchange Commission and the FBI are studying the firm's books, after almost $700 million went missing from customer accounts.
Regulators accuse MF Global of moving the money from clients' accounts in a last-ditch bid to replace its dwindling cash reserves.
More from GlobalPost: FBI joins the probe on MF Global as it enters the spotlight
Corzine said he would continue to assist in the regulatory inquiry. He has not been accused of any wrongdoing, but has hired a criminal defense attorney, the Wall Street Journal reported Thursday night.
He had led the firm since March 2010, after losing a bid to be re-elected New Jersey governor.
MF Global said lead director Edward Goldberg and president and chief operating officer Bradley Abelow will continue in their current positions.
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