The teenager pierced the visitors' offside trap and slotted past Pepe Reina to put his side deservedly ahead.
He added a second when he diverted in a powerful Juan Vargas strike.
Liverpool had chances to get back into the game but Lucas Leiva put a free header wide and Fernando Torres skied a close-range volley.
The Reds did not lose away from home in the Champions League last season but were undone by a poor first-half showing and an inspired Viola at the Stadio Artemio Franchi.
Liverpool had also found the net in their previous 21 Champions League matches and their failure to do so against the Serie A side saw them miss out on Bayern Munich's record scoring run of 22 games.
Fiorentina fielded 19-year-old Jovetic in attack because of striker Alberto Gilardino's absence through suspension and the teenager relished the stage on his first Champions League start.
A bustling and energetic presence in the hole behind fellow forward Adrian Mutu, Montenegro international Jovetic was a major influence as the Italian side took the game to Liverpool after weighing up their rivals.
His reward came when he timed his run to perfection to beat the Liverpool offside trap and latched on to a Cristiano Zanetti pass before cal
mly slotting past Reina.The assured home defence were giving little away as their organisation and discipline created a barrier the Reds struggled to make any impression on.
It gave the Italian side the foundation to push forward with confidence, and their work-rate and movement saw Liverpool struggle to keep them at bay.
The Reds have looked vulnerable in defence so far this season and they conceded a 12th goal in 10 games when Jovetic diverted in a powerful, angled Vargas drive at the near post.
Liverpool had found space and time at a premium as Fiorentina constantly and quickly closed them down and robbed them of possession.
The presence of combative midfielder Javier Mascherano, who is sidelined with a groin strain, was missing but the game changed after half-time.
The visitors increased the tempo and urgency in their play, while Fiorentina sat back and relied on counter-attacks to preserve their lead.
Rafael Benitez's side almost capitalised when Yossi Benayoun cut in from the left byline and had a well-struck shot blocked by keeper Sebastien Frey.
Lucas put a free six-yard header over from the resulting corner when he should have done better and Dirk Kuyt had a shot deflected wide as Liverpool searched for a way back into the game.
Fiorentina were weathering the pressure and Gerrard chested the ball down before having a shot blocked as the home side showed the resolute and stubborn defending Italian teams are famed for.
Torres felt he should have had a penalty after a forceful Alessandro Gamberini tackle late on before he blazed a near-post volley over from a Martin Skrtel cross.
But there was to be no breakthrough for the visitors as Fiorentina held on leaving their fans to raucously celebrate a memorable victory
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