A sweetly-struck set-piece early in the match proved to be the deciding factor as the champions surprisingly slumped to their first defeat of the new season
Despite late pressure from the reigning champions, Hoffenheim held on for a deserved win thanks to some resolute defending and profligacy from the visitors, who couldn't convert their late dominance into a goal.
Hoffenheim began the match brighter, and gave a taste of things to come as early as the sixth minute. Roberto Firmino rattled the crossbar with a shot from just outside the box.
Their early dominance was eventually rewarded minutes later. The hosts took the lead in the ninth minute through Salihovic's rasping 30-yard free-kick which flew into Roman Weidenfeller’s top right corner.
Dortmund’s Shinji Kagawa effort at restoring parity went high and wide of the target after being set up by Mats Hummels. The Japanese midfielder then turned creator as he teed up Kevin Grosskreutz, but the striker’s shot was saved by Hoffenheim goalkeeper Tom Starke.
Mario Gotze then threaded through a inch-perfect through ball for Grosskreutz but the forward was adjudged to have been in an offside position, as the champions sought an equaliser.
Dortmund were again unfortunate not to level matters on the hour mark. Ivan Perisic’s header was denied by the post as he met Chris Lowe’s teasing cross.
Perisic had two more attempts to pull a goal back but, thanks to some dogged defending, neither effort troubled the home side’s goalie.
A late onslaught by the away side saw firstly Robert Lewandowski’s fire inches wide of the post. Then with just two minutes remaining on the clock, Mohamed Zidan set up Jakub Blaszczykowski but his effort was far too high to trouble Starke as the hosts held on for the win.
The victory registers Hoffenheim's first points of the 2011-12 season as Holger Stanislawski’s charges pulled off a surprise win against last season’s title winners.