The Ferrari driver and pre-event championship leader picked up his form from FP1 by also running to the top in the second of the hour-long Friday practice sessions at Barcelona.
Leclerc ran clear on his soft Pirelli C3 tyre qualifying run to 1m19.670s.
That found 0.16s over his benchmark effort from FP1, plus closed to within 0.6s of Hamilton’s pre-season test-topping time at the venue in late February set on the fastest C5 compound rubber.
This moved Leclerc 0.117s clear of Russell, the Mercedes driver having set the pace during FP2 last time out for the inaugural Miami Grand Prix.
Hamilton was a late adopter of the soft tyre and ran particularly well in the final part of the second sector to land the third-fastest effort – albeit a further 0.09s shy of his team-mate.
Meanwhile, ahead of his home race, Carlos Sainz guided the second Ferrari F1-75 to fourth 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 stuck initially to the medium and hard compound tyre.
Sergio Perez and Albon also had their first run of the weekend after missing FP1 as Formula 2 race winner Juri Vips (Red Bull) and Formula E champion Nyck de Vries (Williams) conducted their first GP weekend practice sessions.
Similarly, Zhou Guanyu returned to the cockpit of the Alfa Romeo having made way for Robert Kubica in first practice.
Verstappen had been the first driver to set a fairly representative lap time on medium rubber as he and Sainz dropped below the 1m21s threshold ahead of Leclerc and the Mercedes.
But after only 11 minutes the session was interrupted by a virtual safety car.
That intervention was required when the Alfa Romeo of Valtteri Bottas, running sixth at the time, expired on the home straight after the Finn had completed only three laps.
Valtteri Bottas, Alfa Romeo C42, parks up with a technical problem
Photo by: Steven Tee / Motorsport Images
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