The Monegasque dazzled throughout the Friday and Saturday sessions in Monaco, and built up his speed over the sessions to eventually land on a 1m10.270s - a tenth shy of Lewis Hamilton's record pole time set in 2019.
"It was nice, the feeling after a qualifying lap is always very special here," Leclerc said. "I'm really happy about the lap."
"Qualifying is not everything, as much as it helps Sunday's race we need to put it all together tomorrow. I need a good launch and when we do that, hopefully Carlos [Sainz] can follow me and put us in a 1-2. If we are 1-2 we can control the race."
Piastri ran the Ferrari driver close and became the closest competitor to Leclerc, but was just shy of gazumping him in the battle for pole.
Verstappen struggled throughout the weekend with the ride of his Red Bull throughout the final two sectors, but ultimately came unstuck in the opening sector of his final lap where he narrowly survived a scuffle with the Sainte Devote exit barrier. This nonetheless forced the championship leader to abort his lap, and he thus suffered a drop down the order.
Carlos Sainz grabbed third place, while Lando Norris made it into the top four after recovering from a late breakout from the Q1 relegation zone.
George Russell also outqualified Verstappen as Mercedes seemed in stronger form throughout the Monaco weekend thus far, although Lewis Hamilton could not quite leapfrog the Dutch driver and had to be content with seventh.
Yuki Tsunoda took eighth over Alex Albon, who ran off-sequence in Q3 to claim a lap good enough for ninth, as Pierre Gasly completed the top 10.
Gasly knocked out Alpine team-mate Esteban Ocon in Q2 with a late lap that booked the ex-AlphaTauri driver's place in the top 10 shoot-out. Ocon joined Nico Hulkenberg, Daniel Ricciardo, Lance Stroll, and Kevin Magnussen in the bottom five of the intermediate session.
Fernando Alonso and Sergio Perez were the biggest scalps claimed in Q1, as both drivers were left exposed towards the end of the session by their inability to find a competitive lap.
Alonso's final lap initially set him into 13th, but he slipped down the order as a host of other drivers shook off the pressure to improve at the death of the 18-minute session. This thrust the Aston Martin driver, who came within a whisker of securing pole last year, down into 16th.
Perez spent the majority of the session floundering towards the back of the order and, after falling into the drop zone, could not climb out as his final lap of the session failed to yield performance.
The two were separated by Logan Sargeant, as Sauber duo Valtteri Bottas and Zhou Guanyu propped up the order.
| Cla | Driver | Car / Engine | Time | Delay |
| 1 | Charles Leclerc | Ferrari | 1'10.270 | |
| 2 | Oscar Piastri | McLaren/Mercedes | 1'10.424 | 0.154 |
| 3 | Carlos Sainz | Ferrari | 1'10.518 | 0.248 |
| 4 | Lando Norris | McLaren/Mercedes | 1'10.542 | 0.272 |
| 5 | George Russell | Mercedes | 1'10.543 | 0.273 |
| 6 | Max Verstappen | Red Bull/Honda RBPT | 1'10.567 | 0.297 |
| 7 | Lewis Hamilton | Mercedes | 1'10.621 | 0.351 |
| 8 | Yuki Tsunoda | RB/Honda RBPT | 1'10.858 | 0.588 |
| 9 | Alexander Albon | Williams/Mercedes | 1'10.948 | 0.678 |
| 10 | Pierre Gasly | Alpine/Renault | 1'11.311 | 1.041 |
| 11 | Esteban Ocon | Alpine/Renault | 1'11.285 | 1.015 |
| 12 | Nico Hülkenberg | Haas/Ferrari | 1'11.440 | 1.170 |
| 13 | Daniel Ricciardo | RB/Honda RBPT | 1'11.482 | 1.212 |
| 14 | Lance Stroll | Aston Martin/Mercedes | 1'11.563 | 1.293 |
| 15 | Kevin Magnussen | Haas/Ferrari | 1'11.725 | 1.455 |
| 16 | Fernando Alonso | Aston Martin/Mercedes | 1'12.019 | 1.749 |
| 17 | Logan Sargeant | Williams/Mercedes | 1'12.020 | 1.750 |
| 18 | Sergio Pérez | Red Bull/Honda RBPT | 1'12.060 | 1.790 |
| 19 | Valtteri Bottas | Sauber/Ferrari | 1'12.512 | 2.242 |
| 20 | Zhou Guanyu | Sauber/Ferrari | 1'13.028 | 2.758 |
