In 2000, Al Gore won the popular vote but lost the Electoral College.
But Andrew Jackson in 1824 won the popular vote AND topped the Electoral College, but STILL lost the election.
Candidate, % Popular Vote, Electoral Votes
Andrew Jackson, 41.3%, 99
John Quincy Adams, 30.9%, 84
Henry Clay, 13.0%, 37
William Crawford, 11.2%, 41
Others, 3.6%
Jackson did not get the 50+% needed to win the Electoral College. Clay gave his support to Adams, who was then chosen president by the House of Representatives.