The Reds went into the clash on the back of a six-match winning streak but rarely looked like extending it as Cesare Prandelli's side deservedly claimed the three points courtesy of a first-half double from Stevan Jovetic.
 
It means La Viola are now level on points with Rafael Benitez's men in the Group E table and three behind leaders Lyon who saw off Debrecen in Hungary.
 
The night had begun on a more positive note for the Reds after the City of Florence made huge efforts to accommodate the needs of the travelling Kop with a series of events including a nearby fanzone.
 
Indeed, there was a generous spirit in the air when the game got under way and it was the visitors who threatened first, but Steven Gerrard's through ball for Fernando Torres was slightly over-hit.
 
Seven minutes later and the Reds were almost in again, but this time Sebastien Frey was alert to the danger. The former Inter Milan stopper was quick off his line to pluck the ball out of the reach of Dirk Kuyt after the Dutchman looked set to race onto Torres' lobbed flick.
 
At this point it had been a decent opening 15 minutes for the visitors, but the remaining half an hour of the first period would prove somewhat disastrous as the hosts began to take control.
 
A superb first-time pass from Riccardo Montolivo sent Jovetic rampaging through but just when it seemed he was about to burst the net, Martin Skrtel got across to make a vital block.
 
It could have been little more than a reprieve though, as the hosts came even closer to breaking the deadlock from the resulting corner, when Adrian Mutu's acrobatic volley flew inches over the top following good work by Jovetic on the right edge of the area.
 
La Viola may well have been without the suspended Alberto Gilardino, but the front pair of Mutu and Jovetic were looking lively and almost carved Liverpool open on 26 minutes when the former Chelsea man sent in a drilled cross that the Montenegrin came within a whisker of turning home.
 
The Italian support were responding to their side's positive attitude with a crescendo of noise and within two minutes they were celebrating the opener as Jovetic took advantage of a gap in the Reds' defence to race through and coolly slot the ball beyond Pepe Reina.
 
Fiorentina now had the bit between their teeth and before the Reds could steady the ship they fell two behind on 37 minutes.
 
A sizzling cross-shot from Juan Vargas was met by Jovetic whose instinctive snapshot beat Reina at the near post.
 
It had been a disappointing first-half display from the visitors and all the more frustrating given Fiorentina's poor Champions League record on home turf.
 
Prandelli's side lost all three of their matches at the Stadio Artemio Franchi last season and had not won in the competition in Florence since 2000.
 
If the Reds were going to change that, and the fact the Italians had never lost in their own stadium against an English side, they needed to step up a gear.
 
A fast response was required and Yossi Benayoun came close to reducing the areas within a minute of the restart when he cut in from the left-hand byline and fired a shot into the side netting.
 
Lucas Leiva then powered a free header from a corner just over the top before Torres' goalbound flick was deflected inches past the near post with Frey beaten.
 
The Reds were suddenly the dominant side and Gerrard was the next player to hang his head in frustration when his shot on the turn was blocked after some good chest control in the penalty area.
 
The visitors continued to search for a way back into the game, but when Torres thumped Skrtel's right-wing cross inches past the post, it was obvious it wasn't going to be Liverpool's day.
 
Gerrard went even closer with a trademark curler from distance and a looping header late on, but it wasn't to be, and the Reds will now look to pick themselves up in time for Sunday's crunch match with Chelsea.