Proposed by the ruling conservatives in a consensus decision to avert an early general election, the 75-year-old Papoulias won 279 of 300 votes on Tuesday.
Under the Greek constitution, the president is elected by the parliament. All conservative and socialist deputies as well as two independent lawmakers voted for Papoulias, the only candidate.
The communists and the Left alliance, who have a total of 18 deputies, abstained.
A lawyer, Papoulias was a close aide of Andreas Papandreou -the founder of the opposition socialist PASOK party and father of its present leader George Papandreou.
He will be sworn in as president, a largely ceremonial post, on 12 March.
Papoulias was foreign minister from 1985 to 1989 and from 1993 to 1996 under socialist governments which lost power to Prime Minister Costas Karamanlis's conservative New Democracy Party last March.