Popkov joined the Soviet Army in 1940 and graduated from the Chuguevskaya military-aviation school of pilots in 1941. After graduation from the Chuguev military aviation school in May 1941, he remained to become an instructor with the rank of sergeant. He was soon transferred to a school at Bataisk. Soon after the Germans launched Operation Barbarossa in June 1941, Popkov was posted to a fighter regiment supporting Soviet forces on the Kalinin Front, northwest of Moscow. In March 1942 during the Soviet winter counter offensive, Popkov made his first aerial victory near Lake Ilmen. In his first three months at the front he flew over 100 combat missions and shot down four enemy aircraft. In late 1942 Popkov's unit participated in the defence of Stalingrad. He was wounded three times and shot down twice. He claimed a further five Junkers Ju-52 transports and six Bf. 109 fighters. In August 1943 Popkov took command of a fighter squadron in the 5th Guards Fighter Aviation Regiment of the 295th Fighter Air Division. Flying the Lavochkin La-5, he continued to add to his victory tally, shooting down three Messerschmitts near Kharkov, and three more near Kiev. During service over the Crimea, Leningrad and at the battle of Kursk Popkov flew 478 combat missions and took part in 117 air combats, from which he personally claimed 41 enemy aircraft shot down and 1 victory shared. He eventually became commander of 5th GIAP Guards Fighter Regiment, 207th Fighter Aviation Division, 3rd Mixed Aviation Corps on the South-Western Front, mainly flying the Lavochkin LaGG-3, La-5, La-5FN, and La-7. He was also squadron commander of 5 GIAP, 11th Fighter Aviation Division, 2nd Guards Assault Aviation Corps on the 1st Ukrainian Front. Post war he graduated from the Red Banner Air Force Academy in 1951, and then served with the General Staff Academy to 1964, being promoted to Lt. General of Aviation in 1968. He flew 25 types of aircraft and helicopters during service with the Ministry of Defense, USSR. He then taught at the Military Engineering Academy until 1980. His biography became the basis of the 1973 film Only Old Men Are Going to Battle directed by Leonid Bykov as the prototypes of Comesqa Titarenko a.k.a. Maestro and Kuznechik. A bronze bust of Popkov was erected in 1953 in Moscow on Samotechnaya Square.