Toledo won the Montreal Championship on Sunday, beating Charles Schwab Cup standings leader Perry with a birdie on the third extra hole.
The 50-year-old Toledo swung his fist after he chipped in for birdie on the par-3 10th hole of the Vallee du Richelieu's challenging Rouville course.
"I always celebrate with a left hook," said Toledo, who was a boxer in his native Mexico before switching careers.
That left Perry with a long putt for birdie that went wide to the left.
"When Kenny missed the putt on the third playoff hole I was shocked, really," Toledo said. "I know it was a 20-footer but it was makeable to tie me and I told my caddie whatever happens, happens here."
Toledo and Perry each shot par twice in a row on the first two playoff holes, both of which were played on the par-4 18th.
"I really like Esteban," Perry said. "He's a talented kid. He works hard and I was very proud of him. That was a great shot. I said, 'One of us needs to make a birdie.' Bad for me, but good for Esteban. Great job."
Toledo, who shot a 3-under 69 to finish 5-under 211, won the Insperity Championship in May in Texas to become the first Mexican winner in Champions Tour history. He also won that event on the third hole of a playoff, topping Mike Goodes with a par.
"It's been pretty awesome winning twice as a rookie," Toledo said. "I think I'm going to have a pretty good shot to be the rookie of the year with Rocco Mediate. I wish him the best. He's a really good player."
It was the highest winning 54-hole score on the tour since 2008, when Jerry Pate shot 5-under to win the Turtle Bay Championship in Hawaii.
Perry, who shot a 70, added to his commanding lead over Bernhard Langer in the Charles Schwab Cup standings.
He rode a cart throughout the final round because of pain in his back and his right heel.
"I was just fighting through it," Perry said. "I was just trying to finish. I came all the way up here to finish and my goal was to play 54 holes. I actually played very nicely. I drove the ball beautifully. I drove it better today than I've driven it all week. There is something to be said about the wounded guy. I guess I was more in control, more in reserve, not trying to swing so hard at it."
Duffy Waldorf shot his second straight 70 to finish one stroke back in third.
Langer, who shot a 75, began the day with a three-stroke lead at 6 under. The two-time Masters champion double-bogeyed the par-3 fourth hole and finished in a four-way tie for fourth with Anders Forsbrand, Michael Allen and David Frost.
Mediate shot a 74 to finish 1-over 217 one week after cruising to his second Champions Tour win in Calgary. He shot a 22 under to win the inaugural Shaw Charity Classic by seven strokes.
All three previous Montreal Championship winners finished 3-over 219.
Mark Calcavecchia, who won last year on the Vercheres course, shot a 73, as did Larry Mize, who won the inaugural edition of the tournament in 2010 at Fontainebleau in Blainville, Que. John Cook, who won in 2011 at Fontainebleau, shot a 71.
Rod Spittle of Niagara Falls, Ont., was the top Canadian out of three in the field. Spittle birdied the 17th to finish with a 71 in an eight-way tie for ninth at 1-under 215.
"We get to play some great places throughout the year but to play in Canada for the past two weeks, obviously Calgary and here in Montreal, I've looked forward to it all summer," Spittle said. "I played well last week, I played well again this week, so it's always fun to come home and it's even more special when you play well, so I'm very, very happy."
Victoria's Jim Rutledge shot 7-over 79, including four bogeys and a triple-bogey on the par-4 16th hole, to finish 13-over 229. Marc Girouard of Saint-Sauveur, Que., shot a 74 to finish 17-over 233.Suggest a correction