He flew on the Soyuz 11 mission and had the unfortunate distinction of being part of the second Soviet crew to die during a space flight.

After a normal re-entry, the capsule was opened and the crew was found dead. It was discovered that a valve had opened just prior to leaving orbit that had allowed the capsule's atmosphere to vent away into space, suffocating the crew.

Dobrovolskiy's ashes were inurned in the Kremlin Wall on the Red Square in Moscow.