Serova was born Valentina Polovikova(Валентина Половикова) in 1917 in Kharkiv. In 1938, she married her first husband, Anatoli Serov, a Soviet Air Forcegeneral, a test and fighter pilot. In 1939 Anatoli Serov died in a crash testing a new plane. In the same year, her film "Devushka s harakterom" (eng. "A Girl with Character") had a huge success and she became one of the biggest film stars of the Soviet Union.
In 1940 she met Konstantin Simonov, a famous Soviet author, whom she married in 1943. Simonov's poem "Wait For Me", one of the most famous Russian war poems, is dedicated to her. She subsequently inspired a series of love poems, collected as "With You and Without You" ("С тобой и без тебя"). Their relationship was a troubled one. During the war it was widely rumored that Serova was a mistress of Gen. K.K. Rokossovski. While it's true that Serova, working as a hospital volunteer, met Rokossovski several times while he was recovering from a wound from a shell fragment in early 1942, there is no evidence that they were lovers. Rokossovski already had a mistress at this time, Dr. Lt. Galina Talanova, with whom he had a daughter in 1945.
Her career declined after the 1940s. Simonov left her in 1957. She became an alcoholic and died in Moscow in 1975.