The 50-year-old Toledo 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.
Toledo shot a 3-under 69 to match Perry at 5-under 211 on La Vallee du Richelieu's Rouville Course. Perry, the Senior Players Championship and U.S. Senior Open winner in consecutive tour starts this summer, had a 70.
Toledo, a former boxer, swung his fist after he chipped in for the birdie.
''I always celebrate with a left hook,'' Toledo said.
Perry had a chance for force another hole, but his long putt was wide 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.''
They each parred the par-4 18th twice in the playoff, and Toledo won on the par-3 10th.
''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.''
Perry used a cart throughout the final round because of pain in his back and 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 was a stroke back after a 70.
Bernhard Langer, three strokes ahead entering the round, had a 75 to tie for fourth at 3 under with David Frost, Michael Allen and Anders Forsbrand. Frost had a 70, Allen shot 71, and Forsbrand had a 72.
The 5-under total 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.