With Leclerc and Verstappen still side by side, Perez made it three-wide on the outside and collided with the Ferrari man as he turned into Turn 1.
The incident launched Perez's Red Bull into the air, which damaged the car too much to continue as he pulled into the garage to retire, while Leclerc continued with minor front wing damage.
Perez cut a forlorn figure as he climbed out of his Red Bull but didn't appear to regret his high-risk move as he was only interested in winning in front of his home fans.
"I'm sad without a doubt because today was my opportunity," Perez told Spanish broadcaster DAZN.
"I had a very good start and I was only thinking of winning the race. I didn't want to be on the podium. I've been on the podium two years in a row.
"I saw the opportunity and I went for it. In hindsight, I took a risk, but if I had pulled it off I would have come out of Turn 1 in the lead."
Perez said he didn't anticipate Leclerc to still be on his inside as he hoped to outbrake the Ferrari and swoop around the outside of Turn 1, which would then become the inside for the Turn 2 switchback.
"I didn't expect Charles to brake so late since he was the car in the middle," he explained.
"He had a lot less margin than Max, who was on the inside, and I was the one who could brake the latest because I was on the outside."
Perez's early retirement was the worst-case scenario for the masses of Mexican fans who had given their home hero roaring support all weekend, and barely got to see the Mexican race in anger.
"Yeah, it hurts a lot for them, but I'm going home at ease because I gave absolutely everything," Perez insisted.
"Maybe if I had finished on the podium today knowing that I had the chance to win the race...
"It's sad for all the people, because I wanted to give them the victory no matter what."