Azoulay, 49, came from behind after six rounds of voting to defeat Hamad bin Abdulaziz Al Kawari.
Former French culture minister Audrey Azoulay was selected to head the embattled UN cultural agency Unesco after defeating her Qatari rival by two votes in a cliffhanger election on Friday.
Azoulay, 49, came from behind after six rounds of voting to defeat Hamad bin Abdulaziz Al Kawari, also a former culture minister, by 30 votes to 28 after he failed to pick up support from other Gulf states that are part of a Saudi-led coalition boycotting Qatar.
Azoulay succeeds outgoing Director-General Irina Bokova of Bulgaria, whose eight-year term was marred by financial woes and criticism over Palestine's inclusion as a member.
On Thursday, the US and Israel said they plan to pull out of the Paris-based organisation over its perceived anti-Israel bias.