In 1939 when Poland was invaded and divided by Nazi Germany and the Soviet Union following the Molotov–Ribbentrop pact, Volyn was joined to Soviet Ukraine, and on December 4, 1939, the oblast was organized.
Many Ukrainians rejoiced at the "reunification", but the Polish minority suffered a cruel fate. Thousands of Poles, especially retired Polish officers and intelligentsia were deported to Siberia and other areas in the depths of the Soviet Union. A high proportion of these deportees died in the extreme conditions of Soviet labour camps and most were never able to return to Volyn again.
In 1941 Volyn along with the Soviet Union was invaded by the Nazi Germany's Barbarossa Offensive. Nazis alongside Ukrainian collaborators completed their holocaust of the Jews of Volhynia in late 1942.
Partisan activity started in Volyn in 1941, soon after German occupation. Partisans were involved in the Rail War against German supply lines and were known for their efficiency in gathering intelligence and for sabotage. The region formed the basis of several networks and many members of the local population served with the partisans. The Poles in the area became part of the Polish Home Army, which often undertook operations with the partisan movement.
UPA initially supported Nazi Germany which had in turn supported them with financing and weaponry before the start of World War II. Many served in the various RONA and SS units. Once they became disillusioned with the Nazi program, they independently began to target all non-Ukrainians (Poles, Jews, Russians, among others) for extermination. Some 30,000 to 60,000 Poles, Czechs, remaining Jews, and Ukrainians who tried to help others escape (Polish sources gave even higher figures) and later, around 2,000 or more Ukrainians were killed in retaliation (see Massacres of Poles in Volhynia).
In January 1944 the Red Army recaptured the territory from the Nazis.
In the immediate aftermath of World War II the Polish-Soviet border was redrawn based on the Curzon line. Volyn, along with the neighbouring provinces became an integral part of the Ukrainian SSR. Most Poles who remained in the eastern region were forced to leave to the Recovered Territories of western Poland (the former easternmost provinces of Germany) whose German population had been expelled in accordance with the Potsdam Agreement.
The area underwent rapid industrialisation including the construction of the Lutsk automobile factory (LuAZ). Nevertheless, the area remains one of the most rural throughout the former Soviet Union.