Leclerc climbed to the top of the times in the final third of the hour-long FP1 to eclipse his main championship rival by a slender 0.09 seconds, while Carlos Sainz completed the top three.
George Russell, meanwhile, raced to fourth place in the Mercedes W13 – which this weekend debuted a revised nose cooling duct – as track temperatures soared to 60 degrees Celsius.
However, his seven-time champion team-mate Lewis Hamilton watched the session with team boss Toto Wolff from the pits to make way for F1 rookie Nick de Vries.
Verstappen comfortably set the pace during the first round of fast laps, the Red Bull driver sitting half a second ahead of his team-mate thanks to a benchmark 1m34.991s effort.
It was Sainz who brought out Robert Kubica, replacing Valtteri Bottas in the Alfa Romeo, and Zhou Guanyu on track, with the Ferrari driver initially recording a lap of 1m39.577s.
But that was quickly swept aside by Kevin Magnussen and then Lando Norris, who set a 1m37.604s despite complaining of a spongy throttle feel.
Leclerc improved to 1m37.420s before Verstappen, maintaining training form in 2022, blew the bankers on his first attempt, running to 1m35.727s to find 1.6s over the Ferrari.
Perez went wild by around 0.4s, with both RB18s on a pair of red-walled C4 softs, while the revamped McLaren MCL36 enjoyed a 3-4 – Daniel Ricciardo leading Norris.
Verstappen then cycled to his 1m34.991s to complete the opening gambit at the top, initially drawing 1.1s over Perez to allow the improved Leclerc to quickly split the Red Bull pair.
Leclerc, who trails Verstappen by 38 points, was then promptly pipped by Perez, the Monaco GP winner, who responded to the Scuderia’s threat by closing to within 0.5s of his stablemate.
But the Mexican would soon suffer a high-speed spin at Turn 3 when he collected too much inside curb to upset the car, locking up all four tires as he slowed to narrowly miss the wall.
After a lull midway through the session, with 30 minutes to run, Verstappen emerged on a shiny new set of soft Pirellis to drop the times to 1m34.346s thanks to a particularly strong first sector.
But Ferrari soon found an answer as Sainz buzzed the line in 1m34.268s to find himself eight hundredths clear of his Red Bull rival, the F1-75 struggling in the final sector.
Verstappen responded with 21 minutes to go, setting a 1m34.021s lap, but he left time on the table by going wide through the exit curb at Turn 12 after understeer at a corner.
The Dutch ace would also notice the slow gear changes, although this appears to be related to his kerbs stomping from the Turn 8-9 chicane.
Those brief moments left the door open for Leclerc to clock 1mm33.930s – the only driver to lap under 1m34s.
With drivers sticking to the now-cleaned Pirellis for the rest of the hour, the Monegasque maintained his 0.09s advantage over Verstappen to claim first bragging rights.
Sainz finished 0.3 seconds clear of his pace-setter team-mate and will now serve at least a 10-place penalty after picking up his third control electronics package of the season.
Going over the upper limit of two as a legacy of his disastrous engine fire at the Austria GP, like Leclerc in Montreal, another blow could come if Ferrari changes more engine parts as the event continues.
Meanwhile, Russell was the best of the rest in fourth. The Brit drifted adrift by 0.9s, with the W13 notably lifting its inside wheel as a result of the firm porpoise-fighting setup.
Pierre Gasly made good use of the first significant improvement of the campaign for AlphaTauri, moving up to fifth and ahead of Perez.
The session continued to be a messy one for the Mexican, who faced the chicane and had to stop briefly in the Red Bull garage after his torn visor got caught in the right rear suspension.
The RB18 also has modifications for Paul Ricard, thanks to a revised floor – with Adrian Newey getting on his hands and knees to inspect Verstappen’s bargeboard late on.
Norris drove the restyled McLaren (famous for its new side struts) to seventh ahead of Alex Alban’s Williams, while F2 and Formula E champion de Vries finished ninth – after running wide at the start to risk damage on the floor.
Ricciardo completed the top 10 ahead of Jow, Lance Stroll, Esteban Ocon and Sebastian Vettel.
Behind Fernando Alonso in 15th, consistent points scorer Mick Schumacher edged ahead of Haas stablemate Magnussen, while Tsunoda, Kubica and Nicolas Latifi completed the order.
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