[1] Mustafayev was born on 14 April 1952 in Qazakhbeyli village of Qazakh raion of Azerbaijan SSR.

In 1976, he entered Baku State University and graduated in 1981 with a degree in journalism.

After the graduation, he started working for News program of the Azerbaijani State Television and Radio company.

[1] Mustafayev was killed along with 22 passengers and crew members in a helicopter which was shot down by Armenian forces near the Qarakend village of Khojavend district in Nagorno-Karabakh, Azerbaijan.

[2][3] Ali Mustafayev was buried at a Martyrs' Lane cemetery in Baku.