Before entering politics, he attended the University of Milan and the University of Athens and earned an advanced international law degree from the University of Cologne.
His pre-presidential political offices include member of the Greek Parliament for Ioannina, Alternate Minister for National Defense, and Minister for Foreign Affairs.
The son of military man Gregorios Papoulias, he grew up in Ioannina, Greece. His marriage to May Panou resulted in children named Anna, Vicky, and Fani.
He assumed the Greek presidency under the prime ministerial administration of Kostas Karamanlis.