After completing his fifth grade of school in 1929 he worked in ship construction at a collectively owned facility in his hometown before moving to the city of Kharkhov in 1930.

[1][2] Within the first month of the German invasion of the Soviet Union, Pokryshev scored his first aerial victory - a shared shootdown of a He 111.

[2] Throughout the first half of 1942 he rapidly increased his tally of victories, and on 10 July 1942 he was nominated for the title Hero of the Soviet Union for flying 211 missions and scoring several solo shootdowns, which was awarded on 10 February 1943.

In June 1943 he was made commander of the 159th Fighter Aviation Regiment, which used the Yak-7B; that month he scored his last three confirmed aerial victories.

[4][5] In total he had made 305 sorties, engaged in 38 dogfights, with 18 individual and 9 shared confirmed shootdowns; other sources credit him with more unconfirmed kills.

[6][7] Initially he continued to serve as a regimental commander,[5] and in September 1944 he began he studies at the Air Force Academy in Monino, which he graduated from in August 1945.

[8][9] After graduating from the air force academy in 1945, Pokryshev was made deputy commander of the 7th Guards Fighter Aviation Division.