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Agnese Bonfantini was the heroine of the day for Betty Bavagnoli's side, as she scored twice in the final 20 minutes to completely turn the game on its head.
The Giallorosse, needing to beat their visitors in order to move into the top four at the start of the second half of the Serie A campaign, started strongly and created plenty of chances - only to go behind early in the second half.
Things then went from bad to worse, as defender Heden Corrado received a straight red card after a tussle when she was the last defender.
But Roma would not give up and, after a inspired double substitution from Bavagnoli, came roaring back to take the victory.
Bonfantini, who had missed a couple of decent chances earlier in the contest, made amends on the 70-minute mark, as she arrived on time to lash home Annamaria Serturini's inviting cross.
And less than 10 minutes later she ensured victory would be Roma's - moving the ball out of her feet before hitting a low drive across goal and into the back of the net.
“I had not scored for a while, so to score two in a tough game like this is really a great feeling," Bonfantini told Roma TV.
"I hope to score a lot more with this team.”
The Giallorosse showed their resolve to then see out the rest of the game, restricting Sassuolo to barely one clear sight of goal.
Bavagnoli's decision, following Corrado's dismissal, to bring on both Allyson Swaby and Luisa Pugnali was vindicated - as both players made important cameos.
“Congratulations to my team, today they showed great character against a really tough opponent," Bavagnoli said.
"When we were down to 10, they showed incredible spirit to complete a great comeback.”
The result means the Giallorosse move into the top four in Serie A.
See the best photos from Stadio Tre Fontane in the gallery below.
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