Two-time and defending champion Chadwick held provisional pole after the first runs with a 1m57.725s, ahead of an impressive lap by rookie Tereza Babickova.
But as all drivers adjusted to track conditions, having completed practice over nine hours earlier in the day, the lap times would be brought down with fresh tyres on the final runs.
That ignited a battle for pole between Chadwick and Kimilainen, with the Finn displacing her rival with a 1m56.977s, but the Briton’s final flying effort regained her pole with a 1m56.758s.
It marks the Jenner Racing driver’s first pole at Silverstone in the W Series and continues her stunning start to 2022, having won all three of the races so far this season.
Despite missing out on pole, second place still marked Kimilainen’s best qualifying result of the year and disrupts the British domination at the front of the field.
Abbi Pulling, who qualified and finished as runner-up to Chadwick last time out in Spain, had to settle for third place having fallen over half a second off the pace by the end of qualifying for the Racing X squad.
Beitske Visser produced an eye-catching late lap to jump up to fourth place for Sirin Racing and pushed Alice Powell back to fifth who was continually pinged for track limits on the exit of Copse.
Fabienne Wohlwend was another late improver to take sixth place, directly ahead of CortDAO team-mate Marta Garcia and Scuderia W duo Abbie Eaton in eighth place and Sarah Moore in ninth.
Jessica Hawkins’ poor run of form continued, having finished runner-up in the season opener, as she qualified down in 10th place for Click2Drive Bristol Street Motors. Early pacesetter Babickova ended up dropping to 12th place behind Belen Garcia.
The British round of the 2022 W Series takes place at Silverstone on Saturday starting at 1.25pm BST.
W Series Britain - qualifying result
| Cla | Drivers | Laps | Time | Gap | Interval | km/h |
|---|---|---|---|---|---|---|
| 1 |
 Jamie Chadwick | 13 | 1'56.758 | 181.637 | ||
| 2 |
 Emma Kimilainen | 13 | 1'56.977 | 0.219 | 0.219 | 181.297 |
| 3 | Abbi Pulling | 14 | 1'57.312 | 0.554 | 0.335 | 180.779 |
| 4 |
 Beitske Visser | 13 | 1'57.366 | 0.608 | 0.054 | 180.696 |
| 5 |
Alice Powell | 13 | 1'57.415 | 0.657 | 0.049 | 180.620 |
| 6 |
 Fabienne Wohlwend | 13 | 1'57.441 | 0.683 | 0.026 | 180.580 |
| 7 |
 Marta Garcia | 12 | 1'57.615 | 0.857 | 0.174 | 180.313 |
| 8 |
Abbie Eaton | 14 | 1'57.619 | 0.861 | 0.004 | 180.307 |
| 9 |
Sarah Moore | 13 | 1'57.619 | 0.861 | 0.000 | 180.307 |
| 10 |
Jessica Hawkins | 14 | 1'57.672 | 0.914 | 0.053 | 180.226 |
| 11 | Belén García | 13 | 1'57.761 | 1.003 | 0.089 | 180.090 |
| 12 | Tereza Bábíčková | 14 | 1'57.910 | 1.152 | 0.149 | 179.862 |
| 13 | Nerea Martí | 13 | 1'58.138 | 1.380 | 0.228 | 179.515 |
| 14 | Chloe Chambers | 14 | 1'58.172 | 1.414 | 0.034 | 179.463 |
| 15 |
 Bruna Tomaselli | 13 | 1'58.328 | 1.570 | 0.156 | 179.227 |
| 16 |
 Juju Noda | 13 | 1'59.580 | 2.822 | 1.252 | 177.350 |
| 17 | Bianca Bustamante | 13 | 2'00.642 | 3.884 | 1.062 | 175.789 |
| 18 | Emely de | 13 | 2'01.726 | 4.968 | 1.084 | 174.224 |
