The Swiss driver finally reached the top step of the podium at the 69th attempt at Berlin's Tempelhof Airport Circuit - having led the most laps this season prior to Round 7.
Mueller led home Citroen Racing's Nick Cassidy - a podium returnee for the first time since his Mexico City victory - and Nissan's reigning champion Oliver Rowland at the site of his title triumph.
RESULTS: The 2026 Hankook Berlin E-Prix Round 7
A fascinating tactical encounter with PIT BOOST saw the race lead change hands between several drivers, with engineers scrabbling to balance outright pace and energy use around Tempelhof's uniquely challenging track surface.
Mueller found himself inside the top 10 up to the pit stops, having started sixth, and pushed hard when he emerged from the pit lane - taking six minutes of ATTACK MODE and slicing through the top six to hit the front on Lap 29.
Porsche and Mueller looked to have managed things about as perfectly as could be imagined, with track position and a four second lead having taken P1 - all with four percentage points of usable energy in-hand over those around him.
That cushion proved plenty for Mueller to see it home, with second-placed Cassidy unable to make a real dent as the laps ticked away. Rowland wound up third, polesitter Edo Mortara (Mahindra Racing) unable to convert, settling for fourth - but now atop the Drivers' table.
Andretti's Jake Dennis was left wondering what might have been had he not failed to deploy ATTACK MODE twice as he rounded fifth. Mitch Evans (Jaguar TCS Racing) rounded out the top six.
Just 14 points split the top four in the Drivers' running with Mortara's consistent start to Season 12 yielding top spot after Round 7 ahead of Porsche's Pascal Wehrlein - the German failing to score after a puncture scuppered his chances.
Porsche still head Jaguar in both the Teams' and Manufacturers' World Championship, with the second half of the Berlin double-header set to take place at the same time on Sunday, 3 May.
As it happened...
Mortara led the pack down to the Hairpin from pole, with Rowland jumping Werhlein for P2 off the line. Energy looked to be critical, with temperatures also a push - drivers and engineers looking to conserve from the off. Two laps later Rowland elected to slice by Mortara for the race lead down at the Hairpin.
Zane Maloney hit the front on Lap 6 for the first time in his Formula E career, with the Lola Yamaha ABT drivers keen to press on while others conserved - Lucas di Grassi found himself fifth up from 19th on the grid at lights out.
The lead changed hands by the turn early on, with Guenther cycling to P1 - the DS driver gaining 10 spots from his starting berth.
In the energy stake a third into the race, the Porsche pair had a percent or so in-hand on the leaders as Mortara headed Rowland, Maloney, Cassidy, Guenther, di Grassi, Barnard, Ticktum, Wehrlein and Mueller on Lap 9.
Di Grassi then jumped four drivers in one move at Turn 1 to lead on Lap 11, with Maloney following his veteran teammate's lead to take P2. The Brazilian, approaching the halfway stage, sat among the best in terms of remaining energy and looked to be firmly in the mix ahead of the PIT BOOST window.
The Lolas did cycle back into the pack while Cassidy and Rowland elbowed their way to front - Rowland leading Cassidy, Mortara, Maloney, di Grassi, Ticktum, Barnard, Mueller, Vergne and Guenther.
Ticktum, da Costa, Drugovich and Wehrlein all pitted for their mandatory PIT BOOST stop - yielding 10% extra usable energy for the drivers to use. The Porsche driver's stop, however, was enforced with what looked like a puncture - leaving him dead last.
Nato was the first to take his ATTACK MODE on Lap 23, whilst those around him leapt for PIT BOOST. Mortara initially looked like he had the provisional race lead on Lap 23 as things began to shake out but Cassidy and Maloney were in close company as the trio shuffled in the pack.
Rowland was one of the last to pit, and the overcut handed him the race lead on Lap 26 by half a second over Cassidy as he made his exit from the pit lane.
Mueller started his charge from sixth on Lap 28, with four percent energy in-hand on those ahead and six minutes of his 50kW ATTACK MODE boost to use. Come Turn 1 on Lap 29, he'd sliced by Rowland, Mortara, Barnard and Maloney for P1 as it stood.
Cassidy followed with his jump for ATTACK and mirrored Mueller's progress to take second while the Porsche driver stretched a three second advantage out front.
Lap times tumbled under the minute mark as the drivers teed up a sprint finish. Mueller headed Cassidy, Rowland, Mortara, Evans, da Costa, Barnard, Marti, Maloney and Dennis the top 10 on Lap 31. Two missed ATTACK MODE activation attempts for Dennis ruined what looked like a shot at silverware - with the Brit having managed energy well.
Mueller had four seconds on Cassidy, while Rowland and Mortara in third and fourth held two more minutes of their 50kW, all-wheel drive ATTACK MODE boosts remaining.
The Porsche driver was able to make that advantage count in the run to the flag, heading Cassidy and Rowland home for his first Formula E victory.
Follow the race LIVE on web and in the Formula E app!
Keep across Live Timing – which includes a real-time interactive track map and the ability to follow your favourite driver during every session of every E-Prix – plus highlights, detailed session reports, exclusive interviews, all the standings and results as well as data, insight and reaction from trackside.
LIVE: Follow every lap live, with reaction and coverage at fiaformulae.com/live
Additionally, Formula E’s social media channels, website, and app will provide session reports, exclusive interviews, and behind-the-scenes insights from trackside during the five-day event.
Find out more
GEN4: A new era of Formula E is about to begin
WATCH: How to watch every Formula E race in your country
UNMISSABLE: Watch the brand-new season of 'Driver' on Amazon Prime
CALENDAR: Here's every race set for the 2025/26 Formula E season
FOLLOW: Download the Formula E App on iOS or Android
TICKETS: Secure your grandstand seats and buy Formula E race tickets
HIGHLIGHTS: Catch up with every race from Formula E IN FULL
HOSPITALITY: Experience Formula E and world-class motorsport as a VIP