Freiburg claimed their first win since their return to the Bundesliga to end Schalke's unbeaten start to the campaign.
Cha Du-Ri hit the only goal towards the end of the first half to end a run of two successive defeats for the visitors.
Both sides struggled to create many chances in a disappointing opening 45 minutes at the Veltins Arena.
Freiburg had the first glimpse of goal after 12 minutes when Mohammadou Idrissou dragged Ivica Banovic's cross wide of the mark.
Schalke threatened four minutes later but Ivan Ratkic and Mineiro both saw powerful shots blocked by the Freiburg defence.
Jefferson Farfan then delivered a perfect cross for Kevin Kuranyi, but the striker headed over the crossbar for the home side.
That chance came back to haunt Schalke five minutes before the interval as Cha picked up a pass from Yacine Abdessadki and smashed a right-footed shot into the bottom-left corner.
Kuranyi had the chance to pull Schalke level two minutes after the restart but fired wide of the left post from the edge of the area.
Freiburg responded with a free-kick from Felix Bastians, which was pumped into the six-yard box but headed over by Idrissou.
Schalke continued to waste their openings and Heiko Westermann missed the target with his header following a wonderful cross by Marcio Rafinha.
And Freiburg almost nicked a second goal in the dying seconds on a counter-attack, but Idrissou was unable to provide the finish to the move, shooting just wide of the post.
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