Uber's app lets smartphone users locate nearby part-time drivers for the service, who use their own cars to ferry around passengers, as well as locate yellow cabs in cities like New York.
The service has run into opposition from taxi services and local governments in some cities, due to safety fears and complaints that it can dodge rules taxicabs must follow.
In a blog post, Uber CEO Travis Kalanick compared privately held Uber to a political candidate competing against "the Big Taxi cartel," which has used "decades of political contributions and influence to restrict competition, reduce choice for consumers, and put a stranglehold on economic opportunity for its drivers."
He said Plouffe's "expertise, wisdom, and strategic mindset" is a good choice for the San Francisco-based startup. Kalanick said Uber services have reduced drunken-driving incidents, generated jobs and improved local economies.
Plouffe was the architect of Obama's 2008 presidential campaign and a top White House adviser as Obama won re-election.
He is expected to remain on the board of directors for the Barack Obama Foundation, which is selecting a location for Obama's presidential library, but will depart the advisory board for Organizing for Action, a group advocating for Obama's policies.
Ken Thomas contributed to this report from Washington.