The 39-year-old, pushed by Alexey Voevoda who he won bronze with in Vancouver four years ago, showed his liking for home track ice by establishing a 0.32 second lead with two runs to come on Monday.
Zubkov, who also won a silver in the four-man in 2006, was nine hundredths of a second faster than American Steve Holcomb on run one.
Roared on by a partisan crowd on a foggy night at the Sanki Sliding Centre, he set the fastest time again on his second run, clearly delighted as he raised an arm in triumph before his sled had come to a halt.
Zubkov has a combined time of 1.52.82, ahead of Switzerland's Beat Hefti, who has twice won Olympic bronze.
Holcomb, who won four-man gold four years ago, dropped back to third, 0.04 behind Hefti, after his second run - denting his chances of securing a first U.S. gold medal in 78 years in the two-man competition.
Germany have won the last three editions of this event at the Winter Games but their best-placed sled is Francesco Friedrich in seventh.
Jamaica returned to Olympic action after a 12-year absence with Winston Watts and brakeman Marvin Dixon experiencing a wobble or two but completing both runs to sit 30th and last.