Perez, a French rookie on the LIV Tour, sank 11 birdies in total and birdied his last four holes at Club de Golf Chapultepec in Naucalpan on Thursday to fend off Spaniard Jon Rahm, who drained seven birdies en route to a six-under 65.
"Obviously very happy to finish with four birdies," Perez said.
"First hole, probably got a little bit lucky because I think it rolled through the bunker on the left and then got up-and-down for birdie. The second hole, drove it on and two-putted for birdie. Third hole, hit a great pitching wedge on that really small shelf on the left, two, three feet, so it's nice to have a short putt.
"Then the fourth, hit a 3-wood a bit on the left, as well. I think it just covered the tree and then made it far enough down to have a gap wedge and hit that one stiff, as well. So it was nice to not have to deal with long putts at the end."
As for Rahm, whose parents are at this week's event, he was able to set aside the chatter this week regarding LIV Golf's future and focus on the task at hand.
"Just not really generally wasting my time on things I can't control," Rahm, seeking his second win of the season, said.
"So my mindset was to keep working on the week and operate as normal and keep working on the things that I feel like I needed to be working on and prepare for the tournament. That was it."
American duo Dustin Johnson and Harold Varner III are tied for third at four under, along with England's Ian Poulter, Belgium's Thomas Detry, Zimbabwe's Scott Vincent and South Korea's Minkyu Kim and Younghan Song after all shooting 67s.
Ripper GC skipper Cameron Smith (69) leads the Australian contingent at two under and joint 15th.
Travis Smyth, back for the first time as a wildcard after three LIV events in 2022, had a two-over 73, while Marc Leishman (74), Lucas Herbert and Elvis Smylie (both 74s) also struggled.
Bryson DeChambeau, aiming to become the first player in LIV Golf history to win three straight individual events, is in a tie for 29th after opening with an even-par round of 71.
Rahm's solid effort, along with support from McKibbin and England's Tyrell Hatton (69), has Legion XII on top of the team rankings at nine under.
With AAP.