Promoted Mainz snapped Hoffenheim's four-game winning streak to record their fourth victory in their last six games.
Andreas Ivanschitz gave Mainz the lead after six minutes and Aristide Bance made it 2-0 in the 11th minute. Hoffenheim came into the game with 12 goals in their last three games but they did not score against Mainz until Andreas Ibertsberger's goal in the 87th minute.
Mainz continued their fairytale start to the 2009-10 campaign and sit fifth in the table with 14 points. Hoffenheim remained on the same number of points, one place further up the table.
Mainz grabbed the lead after just six minutes with a superb counter-attack goal. Zsolt Löw sent a cross from the left side to Ivanschitz, whose left-foot volley into the top right-hand corner was simply unstoppable.
The hosts doubled their advantage just five minutes later after some confusion in the Hoffenheim back line, who failed to clear the ball and Bance's header looped over Hoffenheim goalkeeper Timo Hildebrand.
Hoffenheim pushed forward looking to pull one back and Vedad Ibisevic's bicycle kick from seven yards went just over the crossbar in the 28th minute.
Hildebrand had to charge out to stop an attack by Bance eight minutes after the break.
The visitors missed two top chances around the hour mark as Demba Ba's effort went over the crossbar from four yards and Chinedu Obasi's shot from five yards went just left of the post.
Obasi headed just over the goal with 21 minutes left and Ibisevic's goal six minutes later was disallowed for offside.
Hoffenheim finally pulled a goal back with three minutes to play after a corner as Ibertsberger had room to blast into the lower left corner from 17 yards.
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