Ruud van Nistelrooy eclipsed another former Madrid striker, Raul, scoring twice to help Hamburg to a 2-1 home win over Schalke.
The veteran Dutchman opened the scoring a minute after the break and the visitors were dealt another blow when they had Benedikt Howedes sent off on the hour mark, the dismissal also bringing Raul's debut to an end as the summer signing was sacrificed.
The 10 men levelled through Jefferson Farfan with 10 minutes to go, only for Van Nistelrooy to snatch a winner three minutes later.
Werder Bremen started life after Mesut Ozil with a thumping 4-1 defeat at Hoffenheim. Germany midfielder Ozil sealed a move to Real Madrid earlier this week and was sorely missed by his former employers in their opening match of the Bundesliga season.
Torsten Frings put the visitors ahead with a penalty after just three minutes but goals from Demba Ba, Peniel Mlapa, Vedad Ibisevic and Sejad Salihovic won the game for the hosts before half-time.
Both newly-promoted sides, Kaiserslautern and St Pauli, came from behind to win 3-1 away from home.
Kaiserslautern's opponents Cologne had Youssef Mohamad sent off after just two minutes but went ahead six minutes later through Milivoje Novakovic.
The visitors, though, came roaring back with Srdjan Lakic's brace and substitute Ivo Ilicevic's strike all in the last 20 minutes.
St Pauli also left it late, scoring three times in the final seven minutes to beat Freiburg at the Badenova-Stadion.
The Hamburg-based outfit, back in the top flight for the first time since the 2001-02 season, looked to be heading to defeat when Papiss Cisse opened the scoring in the 78th minute.
But Fabian Boll levelled in the 83rd minute before two goals in the last two minutes from substitutes Richard Sukuta-Pasu and Fin Bartels turned the match on its head.
Didier Konan netted a second-half winner as Hannover opened their campaign with 2-1 home victory over Eintracht Frankfurt.
Benjamin Kohler netted for the visitors to cancel out Konstantin Rausch's opener for the hosts and Konan scored in the 75th minute to secure three points.
Mohammadou Idrissou marked his Borussia Monchengladbach league debut with a goal but it was not enough for victory against Nurnberg as their match ended 1-1.
The Cameroon forward, signed in the summer from Freiburg, equalised after half an hour's play after Jens Hegeler put the Bavarian side ahead in the 15th minute.