She fills the post that was vacated last November by the ouster of Mark Everson, the former head of the Internal Revenue Service.
The charity's board of governors demanded Everson's resignation because he had an extramarital affair with an official from a local Red Cross chapter in Mississippi.
Since November, the Red Cross has been led on an interim basis by Mary Elcano, who will return to her posts as general counsel and corporate secretary when McGovern takes over in June.
Everson's departure continued a trend of rapid turnover atop the Red Cross. The two women who preceded him as president both resigned amid friction with the board of governors - Bernadette Healy after the Sept. 11, 2001, terrorist attacks and Marsha Evans in 2005, after the Red Cross' widely criticized response to Hurricane Katrina.
Faced with the perception that it had become too bureaucratic and unaccountable, the congressionally chartered charity then underwent extensive changes. It overhauled its disaster response system and cut its 50-member board by more than half.
The board's chairman, Bonnie McElveen-Hunter, said Tuesday that McGovern "brings outstanding leadership skills from the private sector, coupled with a deep commitment to volunteerism."
McGovern, 56, worked from 1974 until 1998 at AT&T, where she began as a computer programmer and rose through the ranks to become executive vice president of the consumer markets division.
She then joined Fidelity Investments, overseeing a unit serving 4 million customers with $500 billion in assets. She joined the Harvard Business School faculty in 2002.
She also has extensive fundraising experience, a potential asset at a time when the Red Cross is cutting hundreds of jobs at its Washington headquarters while grappling with a $200 million budget deficit.
"It is an honor to be asked to lead the American Red Cross, the helping hand to so many people in times of disaster and crisis," said McGovern, describing herself as "humbled and inspired" by the appointment.