Title contenders Lewis Hamilton and Max Verstappen were behind the two Ferraris in P3 and P4 respectively, in front of Valtteri Bottas and Lando Norris.
With only an hour for the teams to get through their run plans on a circuit where finding ideal track position can be difficult, all 20 drivers were out of the pits within two minutes of the lights going green.
While the first timed laps saw the drivers try to feel their way around as they built up confidence, Verstappen went a full nine tenths quicker than anyone else with a 1:13.961, as he seemed happy with his Red Bull from the start – backing that up even further by going 0.462s quicker on his second flying lap, before Hamilton matched his 1:13.499 to the millisecond on the medium tyres.
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A couple of cars appeared twitchy as their drivers tried to find the limit, with Verstappen having snaps of oversteer out of Tabac and Antony Noghes corners, with home hero Leclerc, who missed most of FP1 with an engine issue, almost sliding into the barriers at Rascasse.
Daniel Ricciardo claimed his early lack of pace compared to Lando Norris was down to the unstable rear of his McLaren, asking his engineers to make tweaks to his set-up.
Williams’ Nicholas Latifi had to engage reverse in his car after a lock-up at the Loews Hairpin – Formula 1’s tightest corner – but the Canadian was able to get going again.
Yuki Tsunoda also scraped into a wall early on to halt his running in the session, crucially hampering his track time on his first ever weekend of driving around Monaco.
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Soft tyre runs started half-way through the session and Hamilton had a dicey moment when he clobbered the sausage kerb at the Nouvelle Chicane, which almost put the World Champion into the wall on the exit of the corner.
Sainz backed up his and Ferrari’s pace from the first practice session by becoming the first driver to dip into the 1:11s, with a 1:11.796 putting him a 0.285s clear of anyone else.
Drivers throughout the field queued up patiently to put in representative lap times and with space at a premium, Mick Schumacher almost crashed into the back of Sergio Perez with the Haas on a flying lap and the Mexican slow on the racing line.
But out of the blue as cars appeared to switch to long run simulations, Leclerc put himself top of the times with a 1:11.684 to form a Ferrari one-two on the leaderboard, with both cars showing an impressive turn of speed around the streets of Monte Carlo.
Where Schumacher had a lucky escape by not running into Perez, his Haas slipped off-line and collided with the barrier at Massenet – dislodging his left-rear tyre, but the young German managed to get to the run-off area at the Nouvelle Chicane and get his car out of harm’s way.
However, the red flag came out and running for the session halted, with both Ferrari drivers sitting right at the head of the field.
(All fastest times set on soft tyres, except Yuki Tsunoda)
1 Charles Leclerc Ferrari 1:11.684 30 laps
2 Carlos Sainz Ferrari 0.112s 32 laps
3 Lewis Hamilton Mercedes 0.390s 28 laps
4 Max Verstappen Red Bull 0.397s 27 laps
5 Valtteri Bottas Mercedes 0.423s 32 laps
6 Lando Norris McLaren 0.695s 23 laps
7 Pierre Gasly AlphaTauri 0.814s 28 laps
8 Sergio Perez Red Bull 1.024s 24 laps
9 Antonio Giovinazzi Alfa Romeo Racing 1.062s 28 laps
10 Sebastian Vettel Aston Martin 1.298s 26 laps
11 Kimi Raikkonen Alfa Romeo Racing 1.381s 31 laps
12 Fernando Alonso Alpine 1.491s 27 laps
13 Lance Stroll Aston Martin 1.511s 26 laps
14 Esteban Ocon Alpine 1.515s 28 laps
15 Daniel Ricciardo McLaren 1.573s 26 laps
16 George Russell Williams 1.825s 32 laps
17 Nicholas Latifi Williams 1.909s 31 laps
18 Nikita Mazepin Haas 2.723s 26 laps
19 Mick Schumacher Haas 2.732s 25 laps
20 Yuki Tsunoda AlphaTauri 3.145s 11 laps