The Ferrari driver and championship leader prior to the event picked up his form from FP1 by also running to the top in the second of Friday’s hour-long practice sessions in Barcelona.
Leclerc ran clear on his soft Pirelli C3 tire qualifying run to 1m19.670s.
That was 0.16s more than his benchmark effort of FP1, plus closed to within 0.6s of Hamilton’s pre-season test-topping time at the late February site on the fastest C5 compound rubber.
That put Leclerc 0.117s clear of Russell, the Mercedes driver who had set the pace during FP2 last time for the inaugural Miami Grand Prix.
Hamilton was a late user of the soft tire and ran particularly well in the latter part of the second sector to put in the third fastest effort – albeit another 0.09 seconds ahead of his teammate.
Meanwhile, ahead of his home race, Carlos Sainz led the second Ferrari F1-75 to fourth place, ahead of defending champion Max Verstappen.
Alexander Albon, Mick Schumacher, both Aston Martins and Esteban Ocon were the first drivers to hit the track in FP2 as the field was initially stuck to the medium and hard compound tyre.
Sergio Perez and Albon also had their first run of the weekend after missing out on FP1, while Formula 2 race winner Juri Vips (Red Bull) and Formula E champion Nyck de Vries (Williams) had their first GP weekend practice sessions.
Likewise, Zhou Guanyu returned to the cockpit of the Alfa Romeo, having made way for Robert Kubica in the first practice session.
Verstappen was the first driver to set a reasonably representative lap time on medium rubber as he and Sainz dropped below the 1m21s threshold ahead of Leclerc and the Mercedes.
But after 11 minutes the session was interrupted by a virtual safety car.
That intervention was necessary when the Alfa Romeo of Valtteri Bottas, then in sixth place, died on the home track after the Finn had only completed three laps.
A cloud of smoke from behind was matched by the engine which seemed to die immediately when Bottas stopped on the edge of the track exiting Turn 1.
After the VSC’s three minutes, the other notable incidents struck Albon and Lando Norris as both ran wide out of the fast turn 9 righthander.
This allowed them to see over the curb, throw gravel and send sparks flying.
Both drivers expected damage to the floor of their ground effect machines, but as Albon continued into the session, Norris was forced to return to the McLaren garage for the remainder of FP2 after completing just six laps.
Albon and Sainz also remain under investigation by the stewards after a close call between the pair at Turn 2.
After 21 minutes came the switch to soft tires and the halo qualifying runs, with Vettel taking first place in the highly updated and controversial Aston Martin AMR22.
His 1m20.703 – then fastest at 0.23s – was soon displaced by Perez, despite the Red Bull driver losing some pace due to traffic in Turn 10.
Verstappen then buzzed the timeline with his 1m20.006s and found a huge margin of 0.7s at the time.
He would remain the fastest driver through the first and last sectors, but fell back during the middle part of the lap.
Then Sainz, the Mercedes and Leclerc set the ultimate times to lead FP2.
Things were less rosy for Leclerc in his race on the late medium tires, however, as he dropped several tenths a lap on Verstappen as he complained about tire behavior and relegation.
Fernando Alonso led his Alpine to sixth in front of his home crowd, while Perez and Vettel advanced to seventh and eighth ahead of Esteban Ocon and Mick Schumacher.
Pierre Gasly was the first driver to miss the top 10, the AlphaTauri chasing the Haas of Kevin Magnussen and Lance Stroll.
Yuki Tsunoda was 14th ahead of Daniel Ricciardo to complete a difficult afternoon for McLaren, while Bottas’ very early bath left him in 16th place ahead of stable mate Zhou.
Norris rounded out the times behind the two Williams, Albon piping Nicholas Latifi.
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