The 30-year-old playmaker converted two penalties in only his fourth appearance this season after a John Anthony Brooks own goal had given the visitors the lead, with Sven Schipplock and Sebastian Rudy adding gloss to the scoreline in the second half.
Volland going close
Hoping to extend their unbeaten run to three, Hertha were looking confident in the opening stages, with Änis Ben-Hatira particularly lively on the right wing for the capital club, threatening the Hoffenheim defence on several occasions, albeit without testing visiting goalkeeper Oliver Baumann.
Schipplock was one of three new players in the Hoffenheim starting XI following their midweek defeat to Bayer 04 Leverkusen, the 1899 frontman firing off a warning shot range, before Kevin Volland saw an effort cleared off the line by the leg of Hertha's Marcel Ndjeng.
Salihovic at the double
With the visitors assuming firm control of the contest, Hertha buckled when Brooks inadvertently directed Volland's cross into his own net. Things went from bad to worse for Brooks and his team-mates when Salihovic converted a penalty after the US international had felled Schipplock shortly after, and Salihovic was at it again six minutes before the break, slotting in from 12 yards after Nico Schulz had fouled Andreas Beck in the box.
Trying to find a way back into the game, Hertha emerged for the second half in positive spirits, enjoying the lion's share of possession against a Hoffenheim side hoping to beat their opponents on the break. Ben-Hatira missed their first chance of note 55 minutes into the game, steering a promising Schulz cross just past the right-hand post.
Hertha head coach Jos Luhukay introduced Salomon Kalou and Valentin Stocker just short of the hour-mark as the home side threw bodies forward, inevitably leaving Hoffenheim space to counter. Thomas Kraft did well to deny Salhovic a third from distance, before Schipplock slotted in a fourth from Roberto Firmino's cross.
The visitors refused to take their foot off the gas in the dying stages, with Rudy adding a close-range fifth after another incisive break involving Firmino to seal the Sinsheim club's biggest ever Bundesliga win on a night to forget for Hertha.
Line-ups and statistics
Felix Seaman-Höschele reporting from the Olympiastadion