Mr Moonves acknowledged relations with three of the women but said they were consensual, adding he had never used his position to hurt the careers of women.
Joseph Ianniello, who has been the CBS chief operating officer since 2013, will serve as president and acting CEO while the board of directors looks for a new CEO. "It is systematic, and it is pervasive in our culture", she said. "And this I know is true to the core of my being: Women can not achieve equality in the workplace or society until there is a reckoning and a taking of responsibility".
The donation, which will be made immediately, will come out of any severance that Moonves, one of the media world's highest paid CEOs, might eventually be given. Six more women accused the 68-year-old executive in a new article released earlier in the day by The New Yorker.
Lawyers were said to be putting the finishing touches on the settlement on Sunday.
Any severance "will depend upon the results" of internal investigations into the harassment allegations, CBS said.
The woman interviewed in the latest story alleges sexual harassment or assault by Mr Moonves between the 1980s and the first decade of this century.
Moonves' allies will surely cast his exit as a corporate coup - a successful effort by Redstone to gain a tighter grip on CBS. Other women alleged he forcibly kissed and touched them in the workplace and, in some cases, retaliated against them professionally for rejecting his advances.
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But Moonves could end up with nothing pending an investigation into allegations of violence against women conducted by law firms hired by an independent committee of the CBS board of directors. The revelations add pressure to exit talks that were already underway at the most watched United States broadcast network.
One of his accusers, Jessica Pallingston, told the Pulitzer-winning journalist Ronan Farrow, who broke the allegations against Moonves in The New Yorker, that such a payoff would be "completely disgusting".
"The appalling accusations in this article are untrue", the executive said, before the announcement of his resignation, adding that he has "never used my position to hinder the advancement or careers of women".
Moonves was an advocate for the traditional broadcast network model when others anxious it was becoming obsolete, but he also launched streaming services for CBS entertainment and news.
Also, six new independent CBS board members, including three women, were named - replacing six outgoing board members, the company said.
The money will be subtracted from from whatever severance is due Moonves - who has held the titles of chairman, president and CEO - after an external investigation into misconduct allegations from a previous New Yorker report reveals its findings. That's not all. CBS is saying that they are withholding all financial packages pending an investigation into the harassment allegations.
"I really felt like this was one of the most sexist places I've ever worked", Sarah Johansen, who previously worked as an intern at CBS for Fager, told Farrow.