The Finn set a 1m34.326s to take pole position for the Dutch round off the back of her win last weekend at Spa – her second in the series.
Despite some confusion around the timing board, which suggested Powell could have taken pole, it concluded that Kimilainen had the top spot.
It puts her back in the mix with Chadwick, who leads the championship with 91 points, and Powell, with 84. Kimilainen currently has 60 points.
Powell will line up in second, with the Racing X driver setting a 1m34.400s, two-hundredths ahead of reigning champion Chadwick.
The pair have endured a season-long battle, with Chadwick having taken three positions to Powell’s two.
W Series Academy driver Nerea Marti will start in fourth, with Abbi Pulling fifth in just her second qualifying session of the season, driving for Puma.
Five minutes into the session, Chadwick topped the times for Veloce Racing, with a 1m36.855s, followed by Irina Sidorkova two-tenths slower.
Photo by: Zak Mauger / Motorsport Images
The session was red-flagged soon after as Fabienne Wohlwend crashed on the exit of Turn 3, running wide and bumping over the kerb before hitting the wall. The incident took off her front-right wheel, snapped her front wing and ended her qualifying session, but she was not injured.
Qualifying resumed around 10 minutes later, but within moments the yellow flag was waved after Irina Sidorkova went off onto the grass at Turn 9, albeit briefly. She is under investigation for rejoining the track in an unsafe manner afterwards.
Kimilainen was second quickest, six-tenths behind Chadwick, with Powell four-tenths behind her in third.
As the times tumbled at the halfway point, Abbie Eaton shot up into third place, before Powell pushed her down into fourth, splitting the Ecurie W cars.
There was a second red flag after Sabre Cook beached her Bunker Racing car in the gravel at Turn 11, with her rear wheels becoming totally sunk in the trap.
Zandvoort W Series – Qualifying results