"Few Americans can boast the breadth of experience that Bill brings to this job," Obama told reporters in the East Room as Daley, 62, stood at his side.
"But most of all, I know Bill to be somebody who cares deeply about this country," the president said.
The appointment represented the most significant move in a far-reaching and ongoing staff shakeup that included the departure of Obama's press secretary and several key deputies and economic advisers. It came the day after Republicans officially assumed control of the House and increased their numbers in the Senate.
Daley, who served as commerce secretary for President Bill Clinton, offers criteria Obama wants for the new environment in Washington: an outsider's perspective, credibility with the business community, familiarity with the ways of the Cabinet and experience in navigating divided government.