The Briton pulled out a margin of more than two tenths in the opening sector during the final qualifying duel before Maserati MSG’s Guenther pulled half of the deficit back in sector two.
The margin came down further in the final sector but Rowland held on to claim his second Formula E pole of the season by just 0.021s with a 1m19.023s.
A 1m18.855s which proved to be the fastest lap from the entirety of qualifying had ensured Rowland progressed to the final at the expense of Edoardo Mortara, as the Mahindra driver fell short by 0.226s.
An error-strewn lap cost ERT’s Sergio Sette Camara as he never troubled Guenther in their semi-final bout, finishing more than two seconds behind at the line.
A small mistake in the opening sector meant Pascal Wehrlein lost more than four tenths against Guenther in their quarter-final duel and although the Porsche driver reduced the deficit, he still missed out by three tenths.
Sette Camara was never headed in his battle against Abt’s Nico Muller, as he finished nearly six tenths clear to progress to the semi-finals.
A scruffy lap meant reigning champion Jake Dennis was slower than Mortara in all three sectors of their quarter-final duel, as the Mahindra driver posted a 1.19.008s to finish three tenths clear.
Mitch Evans’s quarter-final duel almost ended in disaster as the Kiwi glanced the wall through the fast right-hander of Turn 9 and which ultimately cost him in his battle against Rowland.
Evans initially missed out on progressing to the duels by half a tenth after finishing the opening qualifying group in fifth.
The Jaguar driver, who is set to make his 100th race start later today, finished 0.333s behind pacesetter Rowland, with Mortara, team-mate Nick Cassidy and Dennis also setting faster times.
But Cassidy was stripped of his final and fastest effort due to a technical infraction, meaning the championship leader will start 19th.
Also missing out was Antonio Felix da Costa (Porsche), Norman Nato (Andretti), Jake Hughes (McLaren), Lucas di Grassi (Abt), Jehan Daruvala (Maserati MSG) and Sebastien Buemi (Envision).
Guenther headed the second qualifying group with a 1m19.391s as he was joined in the duels by Sette Camara, the Brazilian brushing the wall on the exit of Turn 20 early in proceedings, Muller and Wehrlein.
Envision’s Robin Frijns missed out by 0.030s as he headed Nyck de Vries, the Mahindra driver taking to the Turn 16 run-off on his final effort and lucky not to be collected by Sam Bird.
The McLaren driver lost control just moments later and also headed into the run-off, which left the Sao Paulo E-Prix winner bottom of the group.
Also eliminated were both DS Penske’s of Jean-Eric Vergne and Stoffel Vandoorne, Dan Ticktum (ERT) and the second Nissan of Sacha Fenestraz, who made light contact with the wall on the exit of Turn 2.
