A spectacular individual goal from Aristide Bance in the 69th minute earned Mainz all three points at Hoffenheim.
The home side had looked the more likely to win it before being stunned by Bance, who covered almost 40 yards before scoring the decisive goal which took Mainz up to ninth in the table.
Hoffenheim slip to 11th, 10 points adrift of the top five but too far away from the bottom three to have any relegation worries.
Mainz arrived in Hoffenheim with just one striker, making their intentions clear from the off.
And the home team struggled to break them down with Carlos Eduardo sending his first shot of the game straight into the arms of Heinz Muller.
Vedad Ibisevic, who scored for Bosnia in midweek, was almost on target for Hoffenheim in the 24th minute, but his shot cleared the angle of crossbar and post.
Mainz ditched their more reserved tactics in the second half and started to attack their hosts with Andreas Ivanschitz getting in their first shot of the game in the 64th minute.
However, the Austrian's effort was deflected wide before he sent in a mixture of a cross and a shot moments later which did not result in any danger for the home team.
Mainz went ahead midway through the second period thanks to the individual skill of Bance.
He picked up the ball just inside his own half before starting a determined run through the Hoffenheim defence before pulling the trigger from just outside the penalty area and beating Timo Hildebrand, who still got a touch to the ball, inside his near post.
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