Markus Babbel's team delivered the surprise of the round as they managed to beat BVB, and climb three places ahead of Jurgen Klopp's men
After a quiet first half, the Old Lady stormed into the lead through Rafael, and shortly after doubled their advantage through Peter Niemeyer.
Robert Lewandowski pulled one back for BVB, but it was too little, too late as Jurgen Klopp's men succumbed to their second loss in the league this season.
Dortmund soon began to pick up its game and went close twice through Shinji Kagawa, who saw a right footed drive and a header narrowly miss the target. In a rare counter-attack by the visitors Ramos was again a step late to finish deftly from a cross by Torun on the left.
From there on it was all Dortmund as Jurgen Klopp's men tested Thomas Kraft through Lukas Piszczek and Sven Bender, who both saw long-range drives blocked by the ex-Bayern Munich goalkeeper.
Jurgen Klopp decided to make a change at half-time, sending in Antonio da Silva for the inefficient Ilkay Gundogan. The substitution, however, failed to pay dividends as Hertha Berlin took the lead five minutes after the restart.
Brazilian Rafael found a wide opening in Dortmund's defence and surged forward, skipping past Piszczek and Subotic with ease before seeing his finish from the left side of the box blocked by Weidenfeller. He made not mistake slotting in the rebound, however, as the Old Lady took a shock lead.
Moments later Weidenfeller had to take the ball out of his net again as Niemeyer punished a mistake by Dortmund's defence as forced an Andre Mijatovic past the goal-line to give Hertha Berlin a two-goal cushion.
Lewandowski pulled one back for the champions in the 88th minute when he superbly diverted a free-kick by da Silva into the top left corner with a header to give BVB a lifeline. It was too little, too late, however, as Klopp's men ended on the losing side.
Following today's result, Hertha Berlin is seventh in the standings, while Dortmund sit in 10th place. Markus Babbel's men next league game is at home against Augsburg in a week's time, while the German champions visit Hannover on the same day.