The Dutchman is hunting for his sixth consecutive win this weekend at Silverstone, a feat only completed by four other drivers, as he makes his 150th start for the reigning champions.
Despite struggling for grip in the opening stages, he still managed to take an early lead with a 1m30.443s on the hard Pirelli tyres.
He continued to improve throughout before switching to the soft compound with less than 15 minutes remaining, upon which he set his session-topping time of 1m28.600s, 0.4s quicker than Perez.
With several teams sporting new parts for the weekend – AlphaTauri’s the most drastic – the track was busy early on in the hour-long practice session.
Despite having been running in 14th for the opening 20 minutes, Perez went up into third on the hard tyres before improving to second and demoting Leclerc.
Logan Sargeant was the first driver out on the soft tyres for Williams, slotting into third with a 1m30.327s.
Sainz then followed suit on the red-banded tyres, taking the lead with a 1m29.357s to go 0.5s quicker than Verstappen.
Hamilton was struggling with oversteer on his Mercedes, lacking rear grip at Club as he suffered twitchiness through the apex, with Haas driver Nico Hulkenberg suffering a similar issue.
Russell too had issues, struggling with steering and vibrations at Maggotts and Becketts.
Shortly after the halfway mark, Leclerc went second quickest on the softs, with a 1m29.418s, as the Ferrari pair led the session on the softs ahead of the Red Bull pair running hards in third and fourth.
Though Leclerc improved again to a 1m29.280s, he was unable to hold off the Red Bulls, with Verstappen taking the lead with a 1m28.836s on his first attempt on the softer tyre, 0.4s up.
Perez slotted into second with a 1m29.048s, finishing the session 0.4s off his team-mate.
Fernando Alonso finished fourth for Aston Martin at the team’s home race, with Leclerc fifth and Ocon sixth.
Stroll was ninth, with Oscar Piastri in tenth before suffering a late hydraulic issue in his McLaren.