The Giallorosse took the league champions to extra-time in their clash, but a Cristina Girelli goal with just five minutes to go until penalties ultimately decided the game.
Betty Bavagnoli's side had to overcome too early blows; first Andressa Alves missed the target from the penalty spot, before moments afterwards Barbara Bonansea opened the scoring for the Bianconere in somewhat fortuitous circumstances.
But Roma pushed and probed and created the better chances throughout; eventually getting their reward as Allyson Swaby showed unlikely skill as a striker to run in behind the opposition defence and finish expertly.
Paloma Lazaro went on to hit the bar as Annamaria Serturini also went close on multiple occasions, but it required a late save from Camelia Ceasar - outside the box - to deny Maria Alves a possible late winner on the counter-attack.
That intervention earned Ceasar her marching orders. Bavagnoli's side held on throughout extra-time, before ultimately being undone by Girelli's well-placed header.
Juventus will now go on to face either Fiorentina or AC Milan in Sunday's Supercoppa final.
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