Marium Mukhtiar was born into a Sindhi Sheikh family and she was the daughter of Colonel Ahmed Mukhtiar who settled in Karachi, as his home town. She attended the Mehran Model School and College in Pano Akil and intermediate from Army Public School and College (APSACS) in Malir Cantt, Karachi. She played football for Balochistan United in the National Women Football Championship. She studied civil engineering at NED University before qualifying as a fighter pilot in the Pakistan Air Force (PAF) in 2014, along with six other women. She was also involved in charity work, supporting a school for children who were unable to afford an education.

On 24 November 2015, Mukhtiar and squadron leader Saqib Abbasi were on a routine training mission when their FT-7PG crashed near Kundian, Mianwali, Punjab  Both occupants ejected from the cockpit Abbasi suffered minor injuries, but Mukhtiar died of her injuries in a military hospital.Mukhtiar and her co-pilot had ejected at too low an altitude, an air force spokesman said. Abbasi survived possibly because he had managed to eject seconds earlier.

Mukhtiar's death was declared a martyrdom (or shahadat) by the PAF, which said both pilots "handled the serious emergency with professionalism and courage and tried to save the ill-fated aircraft until the very last minute. Flying Officer Mukhtiar could have saved her life had she ejected before taking PAF FT-7PG out of populous areas but both pilots decided to take the risk to keep flying the falling jet.

She is buried in Malir Cantonment Graveyard.