Lucas di Grassi delivered a composed qualifying lap to take Pole Position on his first Formula E appearance for Mahindra in Mexico.
The season two champion took advantage of an erroneous lap from Andretti's Jake Dennis to take only his fourth career FE pole.
Debutant Jake Hughes finished a remarkable first Formula E qualifying session in third place for McLaren.
A mistake from the second Andretti of Andre Lotterer in his semi-final battle against di Grassi meant he had to settle for a P4 grid slot.
Pascal Wehrlein will line his Porsche up in fifth after losing his quarter-final duel against Dennis, ahead of NIO Racing's Dan Ticktum, who was defeated by Hughes.
Envision Racing's Sebastien Buemi finished the qualifying session in seventh place after losing out in his head-to-head duel against long-time Formula E rival di Grassi by just 0.019 of a second.
Nissan's Formula E debutant Sacha Fenestraz took P8 after narrowly missing out in his duel against Lotterer by 0.044 of a second.
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Big names fall in early qualifying
Both champion DS Penske drivers of Jean-Eric Vergne and Stoffel Vandoorne were two casualties from the first stage of qualifying, with both drivers firmly in the midfield for the race at the shortened Autodromo Hermanos Rodriguez venue.
Antonio Felix da Costa was another big-hitter to fall early from qualifying, the former champion was 0.002 of a second away from progressing into the qualifying duels.
Formula E race winners Mitch Evans (Jaguar) and Edoardo Mortara (Maserati) both missed out on progressing.
Longstanding Formula E racer Sam Bird endured a tough session. The Briton was eliminated in the early stages of qualifying and will start from the back row of the field.