Mihajlović was born in Niš (SR Serbia, SFR Yugoslavia) and began her shooting career at SK "NIŠ 1881" in her native city.

However, individual Yugoslav athletes were allowed to take part as Independent Olympic Participants.

She represented Serbia at the 2008 Summer Olympics in Beijing, People's Republic of China, as she gained qualification for two different events.

She finished 7th in the 50 metre rifle three positions event.

Mihajlović gained her qualification to the 2008 Summer Olympics by taking 4th place at the 2006 ISSF World Shooting Championships in Zagreb, Croatia.