On a return to Venice to forget for the Giallorossi, David Okereke's late goal ultimately decided the game for the hosts.
Goals from both Eldor Shomurodov and Tammy Abraham in the five minutes before half-time had got Roma back on track after Mattia Caldara's third-minute goal - but Mattia Aramu's penalty midway through the second half set the stage for a late winner.
And it was Okereke who ultimately provided it, running clear of the defence before slotting home from inside the box.
Roma will have doubts about both that goal and the early decision to award Venezia a penalty after Caldara tangled with Bryan Cristante - but they nevertheless had chances themselves to score a third goal, with Abraham, Carles Perez and Cristante all going close.
With the international break now taking place, Mourinho and his side have two weeks to prepare for the next match - against Genoa at the Marassi.
VENEZIA 3-2 ROMA
SCORERS: 3’ pt Caldara (3'), Aramu (65' p.), Okereke (74'); Shomurodov (42'), Abraham (45')
VENEZIA (4-3-3): Romero; Mazzocchi (Ebuehi), Caldara, Ceccaroni, Haps; Crnigoj, Ampadu, Busio; Aramu (Tessmann), Okereke (Henry), Kiyine (Modolo)
ROMA (3-4-1-2): Rui Patricio; Mancini, Kumbulla (Perez), Ibanez; Karsdorp (Zalewski), Cristante, Veretout, El Shaarawy (Zaniolo); Pellegrini; Abraham, Shomurodov (Mayoral)
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