Rickey Henderson holds the all-time MLB record for home runs leading off a game, by a wide margin. His 81 are a full 50% more than the runner-up, who has 54. He played forever, led off for his entire career, and was an excellent hitter with solid power who couldn’t be pitched around, so it’s no surprise to see him far and away at the top of this list.
Some of Rickey’s leadoff homers have been especially memorable. When the Oakland A’s were in the 1989 World Series, he hit one to open Game 4 (video).