The reigning world champion, who missed FP1 after rookie Leonardo Fornaroli took part in the session, topped the timesheets with a 1m15.426s, pipping Russell by just 0.009s.
It continued to be tight down to third, with Oscar Piastri finishing 0.057s behind his teammate, leaving the top three separated by less than six hundredths of a second.
Charles Leclerc ended the session in fourth, ahead of world championship leader Kimi Antonelli and Max Verstappen, who spent much of the session focusing on long-run work.
The session began with most of the field heading out on medium tyres, while Verstappen was the early outlier on hards as Red Bull immediately moved into a different run plan.
Franco Colapinto set the first representative lap with a 1m17.766s, but was quickly displaced by Verstappen and Leclerc before Piastri moved to the top with a 1m15.724s.
That put the McLaren driver more than six tenths faster than Russell’s FP1 benchmark, with the pace improving quickly as teams completed their early runs.
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Russell then moved into second with a 1m15.945s, going fastest of all through the first sector but losing time to Piastri across the remainder of the lap.
Antonelli’s first push attempt was less clean, with the Mercedes driver overdoing it into Turn 10 and abandoning the lap before later setting a 1m16.015s.
The session was then interrupted by a virtual safety car when Liam Lawson stopped just outside the pit exit after reporting over the radio that he had lost power.
The Racing Bulls driver was able to get out of the car safely, with his car stranded inside the pit exit lane before it was recovered with an apparent gearbox issue.
The session resumed shortly afterwards, with Verstappen returning to the track on soft tyres while several others began their qualifying simulations.
Leclerc initially moved up to second for Ferrari with a 1m15.799s, helped by a purple middle sector, though his lap still left him behind Piastri’s earlier medium-tyre benchmark.
Piastri then returned on fresh softs and improved to a 1m15.483s, but lost time in the final sector after setting personal bests through the opening two splits.
Norris followed moments later and delivered the eventual fastest lap of the session, producing a 1m15.426s to move 0.057s ahead of Piastri.
Russell responded strongly for Mercedes, but fell just 0.009s short of Norris to split the McLarens at the top of the order.
The top three remained unchanged through the final part of the session as teams shifted attention to longer runs.
Leclerc finished fourth for Ferrari, 0.373s away from Norris, while Antonelli was fifth after a mixed session that later included a trip wide at Turn 10 and a complaint of a long brake pedal.
Verstappen was sixth for Red Bull, having spent time on the hard tyre during the session before asking to end that run early.
“These tyres are horrendous,” Verstappen said over the radio before pitting and returning to the soft compound.
Arvid Lindblad continued his encouraging weekend by finishing seventh for Red Bull, ahead of Gabriel Bortoleto, Lewis Hamilton and Isack Hadjar.
Hamilton finished only ninth in the second Ferrari, having complained during the session that the bottom of the car felt as though it was dragging along the ground.
Nico Hulkenberg was 11th for Audi, ahead of Oliver Bearman, who completed a long stint on soft tyres before switching back to mediums late in the hour.
Lawson returned to the order in 13th despite his earlier stoppage, with Racing Bulls able to repair his car in time for him to complete a practice start at the end of the session.
Carlos Sainz finished 14th for Williams ahead of Colapinto, with Pierre Gasly 16th and Esteban Ocon 17th.
Valtteri Bottas was delayed by an ECU issue on his Cadillac but eventually joined the session after the team reprogrammed the car, finishing 18th.
Alex Albon was 19th in the second Williams after a difficult session in which he asked the team whether it should “box and regroup”, while Sergio Perez was 20th for Cadillac.
Fernando Alonso and Lance Stroll rounded out the order for Aston Martin, with Alonso also placed under investigation for crossing the white line at pit exit.
Cars return to the Circuit de Catalunya for third practice on Saturday at 12.30pm (8.30pm AEST).
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