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.
Alex Albon finished the session third for Williams with a 1m29.089s, sporting a special livery for the team's 800th grand prix.
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.
George Russell put the first time on the board for Mercedes with a 1m33.471s, before he was bettered by team-mate Lewis Hamilton, who went almost a second quicker.
Verstappen then took the lead for the first time as Charles Leclerc slotted into second for Ferrari, though Hamilton was quick to take second again with a 1m31.422s.
The two-time world champion improved to a 1m29.863s to go 1.1s clear of second-placed Lance Stroll (Aston Martin) before the Ferrari pair of Leclerc and Carlos Sainz moved ahead of him.
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.
Sainz, who took his maiden F1 win at Silverstone last year, finished seventh, ahead of home hero Lando Norris (McLaren).
Stroll was ninth, with Oscar Piastri in tenth before suffering a late hydraulic issue in his McLaren.
| Cla | Driver | Chassis | Engine | Laps | Time | Gap | |
|---|---|---|---|---|---|---|---|
| 1 |  Max Verstappen |
 |
Red Bull | Red Bull | 26 | 1'28.600 | |
| 2 |  Sergio Perez |
 |
Red Bull | Red Bull | 22 | 1'29.048 | 0.448 |
| 3 |  Alex Albon |
 |
Williams | Mercedes | 22 | 1'29.089 | 0.489 |
| 4 |  Fernando Alonso |
 |
Aston Martin | Mercedes | 21 | 1'29.268 | 0.668 |
| 5 |  Charles Leclerc |
 |
Ferrari | Ferrari | 25 | 1'29.280 | 0.680 |
| 6 |  Esteban Ocon |
 |
Alpine | Renault | 23 | 1'29.319 | 0.719 |
| 7 | Carlos Sainz |
 |
Ferrari | Ferrari | 25 | 1'29.357 | 0.757 |
| 8 |  Lando Norris |
 |
McLaren | Mercedes | 25 | 1'29.441 | 0.841 |
| 9 |  Lance Stroll |
 |
Aston Martin | Mercedes | 26 | 1'29.471 | 0.871 |
| 10 |  Oscar Piastri |
 |
McLaren | Mercedes | 16 | 1'29.658 | 1.058 |
| 11 | Nyck de Vries |
 |
AlphaTauri | Red Bull | 26 | 1'29.691 | 1.091 |
| 12 | Lewis Hamilton |
 |
Mercedes | Mercedes | 23 | 1'29.768 | 1.168 |
| 13 | Pierre Gasly |
 |
Alpine | Renault | 24 | 1'29.828 | 1.228 |
| 14 | George Russell |
 |
Mercedes | Mercedes | 28 | 1'29.874 | 1.274 |
| 15 |  Valtteri Bottas |
 |
Alfa Romeo | Ferrari | 22 | 1'30.090 | 1.490 |
| 16 |  Yuki Tsunoda |
 |
AlphaTauri | Red Bull | 28 | 1'30.092 | 1.492 |
| 17 |  Logan Sargeant |
 |
Williams | Mercedes | 24 | 1'30.124 | 1.524 |
| 18 |  Zhou Guanyu |
 |
Alfa Romeo | Ferrari | 20 | 1'30.321 | 1.721 |
| 19 |  Kevin Magnussen |
 |
Haas | Ferrari | 21 | 1'30.385 | 1.785 |
| 20 |  Nico Hulkenberg |
 |
Haas | Ferrari | 22 | 1'30.591 | 1.991 |
| View full results | |||||||
