Kolarov - who beat Atalanta on the first day of the season with a decisive free-kick - pulled off the same trick again at Turin's Stadio Olimpico, this time going over the wall as he beat Salvatore Sirigu to break the deadlock in what had been a combative match.
Both sides cancelled each other out for large parts of the contest, with the Giallorossi edging possession in the first half but not always able to turn that into clear-cut chances.
That was until Kolarov turned up, of course, following up Wednesday's brilliant strike against Chelsea with a match-winner here.
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With Federico Fazio missing the game with a slight knock, Di Francesco opted to give Hector Moreno his first start for the club.
The coach made a couple of further changes elsewhere on the pitch, moving Alessandro Florenzi to right-back - and deciding to put Radja Nainggolan and Stephan El Shaarawy in support of Edin Dzeko, with Lorenzo Pellegrini in midfield.
7' - Solid start from the visitors, but Jesus has to be strong to fend off Sadiq as the striker breaks towards goal.
12' - Good pressure from Roma, but Torino's defence clear the danger...
23' - First good chance of the game falls to Dzeko, whose glancing header has Sirigu worried as it just goes wide.
26' - Radja goes for the first-time hit from the edge of the box, but can't keep his strike down...
29' - El Sharaawy spreads the ball brilliantly with a first-time hit... Florenzi runs onto it but lashes wide from 20 yards.
35' - Torino counter quickly through Niang, who feeds Ljajic. But Moreno steps in to make an important block.
43' - Florenzi's powerful clearance nearly catches Sirigu out ... but he tips the ball over the bar!
44’ - The corner evades Sirigu but Strootman has no time to react at the far post and the ball goes wide!
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51' - Roma push forward and Pellegrini swings in a dangerous cross. Strootman meets it but the attempt floats wide.
53' - Radja runs onto Sirigu's poor punched clearance, but again he cannot quite keep his shot down...
56' - Ljajic has room on the edge of the box but his powerful low strike is watched wide of the near post by Alisson.
69' - GOAL! ROMA LEAD! Another away game, another free-kick from Kolarov! The defender curls a brilliant left-footer beyond Sirigu and into the top corner! 0-1!
89' - Roma capitalize on an error and Radja feeds Cengiz ... but he shoots straight at Sirigu!
90' - Bruno Peres dances into the box and lashes a shot that Sirigu is forced to parry away.
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"We’ve achieved a huge victory at a tough place to play; the pitch here wasn’t the best either. We were sloppy with our final ball, but we managed to keep control of the game against a team that cause problems for many other opponents."
- Eusebio Di Francesco
"It was important to get the win today after the tiring match in London [against Chelsea]. We did what we had to do, got three important points and now we need to take advantage of the fixture list which has thrown up two winnable home games."
- Aleksandar Kolarov
Roma now have three straight home games coming up, starting with Wednesday's visit from Crotone to the Stadio Olimpico.
On Saturday they then host Bologna at the same ground, before Chelsea arrive the following Wednesday as the second phase of the Champions League group stage gets underway.
Goalscorers: Kolarov (69')
Torino: Sirigu; Molinaro; NKoulou, Moretti; De Silvestri; Rincon, Baselli; Iago Falque, Ljajic, Niang; Sadiq.
Roma: Alisson; Florenzi (Peres), J. Jesus, Moreno, Kolarov; De Rossi, Strootman; Pellegrini (Cengiz), Nainggolan, El Shaarawy (Perotti), Dzeko.
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