The Russian duo received a mark of 84.17 from the judges and will have the lead when the long program is skated and the medals are awarded on Wednesday.
Aliona Savchenko and Robin Szolkowy of Germany had the second best score with a 79.64 and Russians Ksenia Stolbova and Fedor Klimov were third with a 75.21.
Americans Marissa Castelli and Simon Shnapir were ninth after the short program.
Both of the Russian pairs were part of the first figure skating team event held earlier at these Olympics. Volosozhar and Trankov skated the short program in the team competition and Stolbova and Klimov represented Russia in the long program.
Both of the pairs won their portion of the event as part of a runaway gold medal performance by the Russian team.