The 5-4 shoot-out win exacted revenge for a humiliating 7-1 World Cup semi-final defeat to Germany two years ago.
Olympic gold was the only major title to have escaped five-time world championsBrazil in their history.
But Barcelona star Neymar righted that historical wrong as he fired the winning penalty into the top corner before breaking into tears.
In front of the biggest crowd of Rio’s Games, including nine-time Jamaican gold medallist Usain Bolt, Neymar’s brilliant free-kick handed Brazil a first-half lead.
In honour of the retiring sprinting great, Neymar even adopted the “lightning bolt” celebration, whilst chants of “ole, ole, ole, Neymar” rang around Rio’s most iconic arena.
However, Germany captain Max Meyer enjoyed a special celebration of his own as he taunted the raucous 78,000 crowd at the Maracana by kissing the number seven on his shirt when he swept home Jeremy Toljan’s cross just before the hour mark.
The first eight penalties in the shootout were all successful before Brazilgoalkeeper Weverton stopped Nils Petersen’s effort to set the stage for Neymar.
And he didn’t disappoint as, with the weight of a nation on his shoulders, he rifled the ball into the top corner.
In stark contrast to the empty seats on show across the Games, even at times when Bolt has been running, there wasn’t a seat to be had at the Maracana — where Germany won the World Cup against Lionel Messi’s Argentina two years ago.
However, it was for the 7-1 mauling in Belo Horizonte five days previously thatBrazil were seeking revenge.
None of the players that took to the field that day started on Saturday.
Neymar missed the darkest day in Brazil‘s football history due to two broken bones in his back suffered during a bruising quarter-final win over Colombia.
Yet, the good fortune that escaped Brazil on home soil two years ago was certainly with them in the first-half as Germany were desperately unlucky to go in behind at the break.
Julian Brandt’s fine curling effort came back off the bar, whilst Sven Bender also hit the woodwork from close range.
In between times, Neymar had opened the scoring via the bar with a sumptuous dipping effort from 25 yards for his third goal of the tournament.
Weverton made a fine save from Meyer and Paris Saint-Germain defender Marquinhos was fortunate when his mishit clearance flew inches over his own crossbar.
However, Weverton was beaten for the first time in the competition just before the hour mark when Meyer swept home Toljan’s low cross.
Brazil piled on the pressure in the final half hour of normal time as Gabriel Jesus turned Renato Augusto’s dangerous cross just wide, substitute Felipe Anderson fluffed his lines and Neymar’s effort from distance flew just off target.
The hosts had the better chances in extra-time too as Luan burst clear only to see his shot blocked before Anderson was denied when one-on-one with Horn.
Thankfully for Rogerio Micale’s men they were far more clinical from the spot as Augusto, Marquinhos, Rafinha and Luan all netted to hand Neymar the chance to live up to his billing as the host’s poster boy for the Games.