Nick Cassidy secured Citroën its first Formula E pole position since entering the championship this season at the inaugural Madrid E-Prix.
The New Zealander mastered wet and slippery conditions to defeat Mahindra's Nyck de Vries in the final duel after going several tenths faster.
Antonio Felix da Costa who secured victory last time out starts in third ahead of Nissan's Norman Nato, with mistakes having been made by a handful of drivers throughout qualifying.
Championship leader Pascal Wehrlein was one of those to make a costly mistake, resulting in sixth on the grid at the Circuito del Jarama.
Duels
In the final duel, Cassidy had the edge across the entirety of the lap, with de Vries' hopes of pole having been blown by going wide at Turn 7,
To reach the final, de Vries first defeated reigning world champion Oliver Rowland in the quarter finals after the Nissan driver spun at the third corner, before beating da Costa in the semi finals.
As for Cassidy, he narrowly beat Edoardo Mortara by just 0.047s to progress to the semi finals, where he comfortably beat Nato after the Frenchman went off at Turn 7.
In the other two quarter finals, da Costa destroyed former Porsche team-mate Pascalk Wehrlein by 4.4s, while Nato beat Maximilian Günther by 5.2s after the German also went off at Turn 7.
Group stage
The group stage of qualifying got underway on a wet and slippery surface following consistent light rain, which started to fall early Friday evening.
Conditions had worsened since second practice two hours prior, making for a difficult start to qualifying for the drivers.
In the opening group, de Vries led the way on a 1m 41.926 and was joined in the top four positions by da Costa, Wehrlein and Rowland. The quartet progressed to the duels. Home hero Pepe Marti missed out and starts from the sixth row.
Lap times improved considerably in the second group, with Nato topping the group after setting a 1m 40.927. Mortara, Cassidy and Günther joined him in the top four to progress to the duels.
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