Vinikurov, 38, of Kazakhstan, has retired from cycling once and is likely on the verge of retiring again, but his vast experience was enough to overcome his age in the grueling race that began and ended in front of Buckingham Palace.
He broke free from the leading pack in the final two miles and took Colombia's Rigoberto Uran with him.
Together they opened enough of a lead that ensured one of them would win the race and when Vinikurov made his final move Uran could not keep pace.
Alexander Kristoff of Norway won the sprint among the trailing pack and thus captured the bronze medal.
The race was a disappointment to the British team and the thousands who lined the route. British sprinter Mark Cavendish had been the pre-race favorite, having won three stages of the recently-completed Tour de France.
Cavendish had a strong team supporting him, including Tour de France winner Bradley Wiggins. A breakaway group of 32 riders, however, left the British behind during the second half of the race and once the gap grew close to a minute it remained there for the rest of the journey.
Fabian Cancellara of Switzerland, silver medalist in this race four years ago, was another who missed a chance at victory.
He was part of the leading group and was actually out front of the pack when he crashed with about five miles remaining. He failed to properly negotiate a sharp turn and he slammed into a metal barrier on the outside of the curve.
Cancellara soon climbed back on his bike and finished the race, but a layer of skin was peeled away from his left elbow in the fall.