In 1996 Dimitrijević received a PhD from the University of Belgrade's Faculty of Economics. He was co-minister of finance in the transitional Government of Serbia in 2000. He was member of Vuk Drašković's Serbian Renewal Movement (SPO). During the 2005 breakup of SPO when a faction left the party to form Serbian Democratic Renewal Movement (SDPO), Dimitrijević did not take a side.
He is married and the father of one child.