Mercedes-EQ's Stoffel Vandoorne sealed Julius Baer Pole Position by just 0.028 seconds from reigning champion Antonio Felix da Costa (DS TECHEETAH) and his Mercedes teammate Nyck de Vries - though the Dutchman will start eighth following a grid penalty.
Vandoorne squeezed everything out of his Silver Arrow 02 to dart to the top of the times in Super Pole - and stayed there. Da Costa's earlier effort looked quick and tidy, and good enough for the benchmark, but ultimately he fell narrowly short. Promising again, though, for the new E-TENSE FE21.
De Vries was first to run in the Super Pole shootout and did manage the quickest time of the day up to that point. It was enough for third, but a five-place grid penalty - his punishment for clashing with Sam Bird (Jaguar Racing) and Oliver Rowland (Nissan e.dams) in Rome - sees him start eighth.
BMW i Andretti Motorsport's Maximilian Guenther looked to be a good bet for pole prior to qualifying, having set the pace in practice, but the young German would have to settle for a net third - 0.4 seconds off Vandoorne's best.
Alex Lynn (Mahindra Racing) was the quickest driver in Group Qualifying having produced a surgically precise effort, but the Brit couldn't replicate his earlier effort and will line up fourth.
Nissan e.dams' Sebastien Buemi followed in a net fifth with a small lock-up into the tricky final chicane proving costly.
Porsche's Andre Lotterer, Norman Nato (ROKiT Venturi Racing), Rowland, and Pascal Wehrlein (TAG Heuer Porsche) rounded out the top 10.
The standings top two find themselves back in the pack with it all to do; Bird down in 21st and Jaguar teammate Mitch Evans 18th.
The 2021 DHL Valencia E-Prix Round 5 is up next at 15:00 local time.