After having served in the Soviet Navy during World II, including at the Siege of Leningrad, Pavel Kharin got his start in international canoeing after the conflict. Prior to taking up that sport, he had tried his hand in football, volleyball, skiing, and track and field athletics. He made his international début at the Olympics in 1952, where he finished 10th in the C-1 10000. He was much more successful four years later, however, winning the C-2 10000 and coming in second in the C-2 1000, both with Gratsian Botev. The following year he won the C-2 1000 and took silver in the C-2 10000 at the European Championships, both times with Aleksandr Silayev, as Botev had become ill and could not compete. Nationally, he won four titles across various distances between 1956 and 1960. For his achievements, he was awarded the title of Honored Master of Sports in 1957 and, by career, he was a factory worker.