The Kiwi headed the times for nearly half of the 30-minute session on Saturday morning as he gradually lowered his best time down to a 1m13.606s with his final effort.
He finished just 0.064s clear of Maximilian Guenther as the Maserati MSG driver jumped up to second in the final moments, demoting Envision’s Robin Frijns down to third.
Evans’s Jaguar team-mate Nick Cassidy finished fourth, with Sebastien Buemi in the second Envision making it four Jaguar-powered machines inside the top six as DS Penske’s Stoffel Vandoorne split the pair.
Reigning champion Jake Dennis was the first driver to dip below the 1m15s mark, posting a 1m14.914s before heading into the run-off area at Turn 1 as his time was quickly surpassed by Buemi, Nissan’s Oliver Rowland and Guenther.
The Andretti driver was not the only one to overstep the mark into the first turn, with fellow Briton Sam Bird doing similar just minutes later as both rejoined unharmed.
With the track temperature constantly rising and the racing line becoming grippier, times continued to tumble in the opening 15 minutes of the session as Dennis led at the halfway point with a 1m14.221s.
Cassidy moved to the top of the times with a 1m14.014s shortly after, before former team-mate Buemi lowered the benchmark by 0.010s.
Cassidy immediately responded, becoming the first driver to dip below the 1m14s mark but his time was deleted after running over track limits at the final turn.
It was left to team-mate Evans to move to the top with a 1m13.809s heading into the final 10 minutes of the session before lowering the benchmark to a 1m13.626s and subsequently a 1m13.606s.
Less than a second covered 21 drivers, with Nyck de Vries finishing last and 1.186s off the pace on his Formula E return with Mahindra.
Sergio Sette Camara was the only driver in the session to find the barrier, losing control on the entry to the Peraltada and damaging the front wing on his ERT machine.
The Brazilian crashed at almost the same spot in Friday’s shakedown before recovering to the pits both times.
Mexico City E-Prix – FP2 results:
Jake Hughes had topped Friday evening’s opening practice session with a 1m14.364s before the McLaren driver immediately crashed on the exit of Turn 1.
The incident brought out a second red flag which ended the session a few minutes early, with McLaren forced to change the damaged chassis overnight.
An earlier stoppage had been caused when Guenther found the barrier on the outside of the Peraltada, the Maserati MSG driver damaging the left-rear wheel on his machine after less than 10 minutes of running.
The red flags caused further issues post-session as Evans and Cassidy, as well as Vandoorne, were slapped with one-place grid drops for today’s Mexico City E-Prix.
This was after all three failed to follow red flag procedure as each car “did not enter into its garage” after returning to the pitlane.
Another issue to arise from FP1 was with regards to the fast-charging pitstop technology, which was tested by teams during the session, but unforeseen problems meant the concept was not trialled further in Mexico City.