After going behind to Leonardo Pavoletti's first goal of the campaign, Roger Ibanez equalised with a pinpoint header from a corner - before Pellegrini stepped up and dispatched a free-kick into the top corner to decide the contest.
With Jose Mourinho watching on from the stands, the Giallorossi successfully saw out the final moments of the game to complete the ideal preparations for Sunday's meeting with AC Milan.
Matches between these two sides at the Sardegna Arena have traditionally been dramatic affairs, and this one was certainly no different. The first half may have lacked goals but it did not lack for important moments: as Bellanova hit the bar for the hosts and Tammy Abraham went close at the other end.
The breakthrough arrived early in the second half, instead, as Pavoletti put himself in the right place at the right time to steer home from close range.
Roma responded to that setback manfully, however, pouring forward as Pellegrini hit the crossbar and Gianluca Mancini saw another close-range chance dribble agonisingly wide.
Defensive partner Ibanez ultimately showed them both how it was done: steering his header from a corner in off the far post to shift the momentum of the game completely.
Soon after a foul on the ever-dangerous Nicolo Zaniolo presented the visitors with a dangerous chance 20 yards out - a chance Pellegrini duly made the most of.
CAGLIARI 1-2 ROMA
SCORERS: Pavoletti (52'); Ibanez (71'), Pellegrini (78')
CAGLIARI (4-4-2): Cragno; Zappa, Ceppitelli, Carboni, Lykogiannis; Bellanova, Grassi (Oliva), Marin, Deiola (Keita); Pavoletti, Joao Pedro
ROMA (4-2-3-1): Rui Patricio; Karsdorp, Mancini, Ibanez, Vina (Afena-Gyan); Cristante, Veretout (Kumbulla); Zaniolo (Calafiori), Pellegrini, Mkhitaryan (El Shaarawy); Abraham
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