Bayern Munich twice came from behind to draw 2-2 with Borussia Dortmund before goalkeeper Sven Ulreich was their penalty shoot-out hero in the DFL-Supercup.
Pierre-Emerick Aubameyang appeared to have given Dortmund victory after a close-season of speculation linking him to a move away from Signal Iduna Park - the 2016-17 Bundesliga top scorer finishing with aplomb in the 71st minute.
But Peter Bosz's side were unable to hold out during the Dutchman's first competitive game in charge as an 88th-minute goalmouth scramble concluded with a Roman Burki own goal.
Joshua Kimmich instigated Bayern's late leveller but the young Germany star was the first man to falter in the shoot-out, although Ulreich responded by denying Sebastian Rode.
With the score tied at 4-4, Niklas Sule blasted into the top corner for the Bundesliga champions and Ulreich guessed correctly to thwart Marc Bartra.
It meant a welcome fillip for Bayern boss Carlo Ancelotti, who saw his side lose four out of five pre-season friendlies going into a match where they needed Robert Lewandowski to cancel out Christian Pulisic's opener.
It was Lewandowski who fired over shortly before the lackadaisical play evident from Bayern over recent weeks was again on display as Dortmund took a 12th-minute lead.
Arturo Vidal seemed partially surprised to receive a quickly taken free-kick and swept a risky pass across the backline to Javi Martinez.
The Spain international's sloppy touch was the only invitation Pulisic needed to pinch possession, bear down on goal and slot clinically past Ulreich.
Dortmund's lead lasted only six minutes as two stars of Germany's triumphant Confederations Cup campaign combined.
Sebastian Rudy lifted a raking pass over the home defence and Kimmich - amid suspicions of offside later absolved by VAR - tore around teenager Dan-Axel Zagadou and supplied a low cross for Lewandowski to net an eighth goal against his former club.
Gonzalo Castro might have restored Dortmund's advantage but Ulreich was equal to his flicked finish after fine work from Mahmoud Dahoud.
Ulreich's opposite number Burki reacted brilliantly to thwart Thomas Muller at close quarters but was grateful to see a header from the Germany forward spin to safety off his left-hand post 10 minutes before the interval - Kimmich again having caused having havoc, with Bayern's early struggles a fading memory.
Dortmund chief executive Hans-Joachim Watzke told Eurosport before the match that Ousmane Dembele was worth more than EUR100million but the reported Barcelona target turned in an ineffective first-half performance and sliced a volley woefully wide in the 48th minute.
Bayern newboy Corentin Tolisso was unable to find the elevation to beat Burki midway through an often-scrappy second half before some rare indecision from Lewandowski in the area was instantly punished by Dortmund.
The Poland star elected to square having broken free of the defence and, having snuffed out the chance, Bosz's men broke in lethal fashion - substitute Rode fed Dembele, whose pass was perfectly weighted for Aubameyang to lift an impeccable finish into the top corner.
There was a late twist as full-time approached when Kimmich's shot ricocheted over the line via Burki and the Dortmund man would not be the goalkeeper celebrating at the end.