Annan's chief of staff Mark Malloch Brown announced Dujarric's appointment at the UN daily press briefing on Monday.
Dujarric, who has been promoted from deputy spokesman, replaces Fred Eckhard, who is retiring.
Dujarric spent nearly ten years at ABC News and was a foreign correspondent at the network's London and Paris news bureaux.
He travelled extensively across Europe, Africa and the Middle East as an assignment editor and field producer for ABC.
UN associate spokesman Marie Okabe is now Annan's deputy spokesman.
Malloch Brown told journalists at the press briefing he hoped he could count on Dujarric and Okabe to 'live up to (Eckhard's) tradition of trying to be as collaborative as possible'.