The winger was in fantastic form with three assists and a goal to show his new club's fans that there are plenty reasons for optimism after his summer switch from Spain.
In Lionel Messi's absence, Di Maria was given freedom to roam by new coach Gerardo Martino and popped up all over the place in a typically energetic performance. From a position on the right, the winger picked out Sergio Aguero with an impudent curling pass through the German defense with the outside of his left foot to leave the Manchester City man with a simple finish to open the scoring.
Also from the right, the 26-year-old then cut back another cross for Erik Lamela to make it two on the volley, before setting up Federico Fernandez with a set piece from the left early in the second half for 3-0 and adding another himself as he raced onto a ball from Pablo Zabaleta and chipped an exquisite finish past Roman Weidenfeller in the German goal three minutes later.
It was a performance of sheer brilliance that showed Madrid exactly what it will be missing following his summer sale to United. It is almost impossible to defend against the winger in full flight and many fans of the Spanish side will wonder why their club didn't make a bigger effort to retain the 26-year-old.
The midfielder's dynamic display will also have left Argentines wondering what might have been. When these two teams met in the World Cup final back in July, the winger was missing through injury and the Albiceleste lost late in extra-time to Mario Gotze's goal at the Maracana. With Di Maria in the team, things may have been different.
Not that Manchester United or its fans will care about any of that. What they will be concerned with is what he can do for their club and, on this evidence, he will be a huge asset.
A report by independent study center CIES claimed this week that United had paid 30 million euros over the odds for Di Maria, estimating the player's true market value to be around €45m. In this kind of form, however, he is worth every penny of the €75m United paid Madrid for his services.