Faxon had seven birdies as the duo combined for a 10-under-par round in the better-ball team competition at the Club at Savannah Harbor.
"I felt like I rode Secretariat all day," Sluman said of playing with Faxon. ""All I kept saying was 'Good putt. Great putt. Another one.'"
Champions Tour points leader Bernhard Langer and teammate Tom Lehman were next and will be paired with Faxon and Sluman in Saturday's second round of the 54-hole event.
Eight-time major champion Tom Watson and partner Andy North finished the opening round in a three-way tie for third at 8-under. Craig Stadler and Kirk Triplett also teamed for a 64, along with Tom Kite and Gil Morgan.
Faxon's birdies included four measuring 12 feet or longer. One of his shorter putts, an eight-footer, started a run of five birdies in the final six holes. That birdie came on No. 13, a 595-yard par-5 that haunted the duo in their first Legends together last April. They failed to birdie that hole in six tries—three each—and ultimately lost the tournament by two strokes.
"I always have this dream I'm going to play 54 holes with Jeff and never help him," Faxon said. "We did a good job of getting both balls in play and a lot of holes we had two putts for birdie on."
While Faxon carried his partner to the top of the leaderboard, Langer and Lehman's 9-under-par 63 was more a joint effort. Langer accounted for five of the nine birdies—two in the first three holes and three more at Nos. 16, 17 and 18—while Lehman had his birdies in the middle of the round to sustain the momentum.
Langer, coming off his 18th career Champions Tour win last week at the Greater Gwinnett Championship in suburban Atlanta and an impressive three-day run at the Masters the week before, admitted he gave his partner "more gray hair" during an ugly stretch.
"I don't know if either of us can say we played our very best," Lehman said. "It was a good partnership round."