Popkova began competing at the top level in 1965: she won her first Soviet title that year, running over 200 metres, and placed third in the event at the 1965 European Cup. She established herself as the Soviet Union's top female sprinter the following year by winning the national indoor title in the 400 metres then taking a 100/200 m double at the outdoor national event. At the 1966 European Athletics Championships she took the bronze medal over 200 m (finishing behind Polish duo Irena Kirszenstein and Ewa Kłobukowska) and got her second of the competition with the Soviet 4×100 metres relay team which finished third.