Stuttgart made it two wins out of two to inflict the first home defeat on Hertha Berlin since April 2012.
Christian Gentner scored the only goal of the game early in the second half as the Swabians continued their resurgence since Thomas Schneider replaced Bruno Labbadia as coach nearly three weeks ago.
The win lifts Stuttgart into the top half of the table, just a point behind their opponents, who could drop out of the top six this weekend.
Hertha, who opened the season putting six past Eintracht Frankfurt on home soil, appeared willing to prove how much of a fortress the Olympiastadion is.
Not since the 2011/12 season had Hertha lost on home soil, and that record looked like it would remain intact as the enterprising Anis Ben-Hatira led their frequent forays forwards.
Stuttgart spent much of the first half an hour on the back foot, but as soon as they had managed to stifle Hertha's attacking threat they started to create chances of their own, with Gentner going agonisingly close to heading them in front.
Thomas Kraft made a stunning reflex save to deny the Stuttgart captain's header from Alexandru Maxim's corner.
The same combination provided a different result early in the second half as Kraft this time could not get close to Gentner's header, which put Stuttgart in front.
Hertha's reply was instant and Per Skjelbred nearly marked his debut with a goal, but an instinctive one-handed save from Sven Ulreich denied him.
Ulreich then took centre stage, denying Johannes van der Bergh with his legs before tipping Anthony Brooks' header over the crossbar with lightning reflexes.
Peter Pekarik then wasted a glorious chance to level with the last touch of the game, but he failed to make a good enough contact at the far post as Ulreich was relieved not to need to intervene for once.