Evans had made his way to his first final duel of the season by virtue of dispatching Lucas di Grassi and Jean-Eric Vergne on his road to the shootout for pole, and immediately made an impression by going a tenth faster than Wehrlein in the opening sector.
His advantage then continued to grow, standing at 0.225s following the close of the second sector, and looked set to have pole locked in.
Wehrlein's 1m30.096s lap was still among the quickest within the session, marginally slower than his own benchmark in his semi-final duel against Stoffel Vandoorne, but Evans surged to a 1m29.839s to confirm his superiority. Wehrlein's lock-up at the Rascasse decided in favour of Evans, who takes his first pole of the year.
Evans beat Vergne by over a tenth in their semi-final bout, retaining an advantage through all three sectors to leave the French driver out of luck in his bid to make the final. The Kiwi has booked his semi-final place with a 0.285s advantage over di Grassi, although the Brazilian set the fastest time among those knocked out in the first part of the duels.
In the meantime, Wehrlein had claimed his place in the qualifying final after beating Vandoorne by almost two tenths, building a margin to that tune in the opening sector of the lap.
Vandoorne managed to hit back in the middle sector, chipping away half of his deficit in a bid to give Wehrlein a run for his money, but a much tidier final sector for Wehrlein cemented a front-row start as he put space between himself and the Mercedes driver.
Wehrlein was drawn against Porsche team-mate Andre Lotterer in their quarter-final, and it began inauspiciously with contact with the wall at Sainte Devote. But Wehrlein rallied, overturning a sector 1 deficit to ultimately overcome Lotterer by over a quarter of a second, setting a 1m30.098s to Lotterer's 1m30.366s.
Of the other quarter finals, Vandoorne beat Robin Frijns in a duel that initially looked closely contested, with Frijns ahead by the close of the first sector. But the Mercedes driver found a hatful of time in the middle sector, turning the tables with a near-0.3s lead ahead of the final sector, which he largely preserved to stamp his semi-final card.
Vergne brushed Nyck de Vries aside to make it through to the semi-finals, as the 2020-21 Formula E champion struggled to hustle a slightly wayward car through the lap - almost having a moment at Portier to ship a considerable amount of time to Vergne.
On the grid for the Monaco race, Vergne will start ahead of Vandoorne on the second row of the grid as the DS Techeetah driver set the better time in the semi-finals by 0.15s.
Di Grassi starts fifth from Lotterer, with a double-Dutch fourth row as Frijns starts from seventh and de Vries will kick off from eighth.
Sam Bird and Edoardo Mortara were the biggest scalps claimed in Group A, the former getting knocked out by 0.013s having been shaded by di Grassi in a late-session flurry of times.
Dan Ticktum was briefly in second on his final run of the session, but his time was unable to withstand a late onslaught from the traditional frontrunners and dropped to seventh in the group - but outqualified Edoardo Mortara who only placed eighth.
Nick Cassidy had been the top four following the first set of runs, but the Envision driver went off at Turn 1 and ended his hopes of making the duels.
Antonio Felix da Costa was dumped out in Group B after topping second practice, having been shuffled out of the top four by Oliver Rowland - who in turn was deposed by Lotterer who continued his streak of appearing in every duels session so far since this season's qualifying reformat.
Jake Dennis was outqualified by Avalanche Andretti team-mate Oliver Askew, after the British driver repeated Cassidy's Turn 1 faux-pas to end his chances of advancing to the duels.
Rowland begins the race from ninth on the grid ahead of da Costa as Bird - who would have started from 10th - takes a three-place grid drop for his contact with Cassidy at the second Rome E-Prix.
Formula E Monaco E-Prix - Starting grid:
