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The 29-year-old went solo from the seven-strong breakaway of the day 30km out from the finish, holding off the chasers in difficult conditions to win his second career stage of the Giro d'Italia and his team's second at the race in 2024.
Pelayo Sanchez (Movistar) finished in second, 54 seconds behind Vendrame with Georg Steinhauser (EF Education EasyPost) third and Luke Plapp (Jayco-AlUla) was the standout Australian performer of the day with a fifth-place finish.
"It's a nice day today," Vendrame said after the stage. "The important thing was to get in the breakaway. I was there right from the start."
"I thought that somebody was going to come back, but I tried to keep a high rhythm, a regular rhythm. They looked after me very well from the car and it was perfect."
The GC favourites took it easy the day before Stage 20, the final big mountains test, as they came in to the finish together 16 minutes behind Vendrame.
But it could have been on for the podium minor placings late in the stage, after 3rd overall Geraint Thomas (INEOS Grenadiers) came down in an erroneous crash with 6km to go.
As the Welshman waited for his team car and a new bike, the contenders looked at each other but ultimately decided to wait for him to return instead of pushing up the road, a sign of respect and sportsmanship for the former Tour de France champion.
Stage 20 is sure to be a different story though, with action amongst the contenders a near certainty in the last chance to make up time before the processional closing ride through Rome in Stage 21.
"There's another stage to come tomorrow in the mountains," Stage winner Vendrame said.
"We know that Pogi [Tadej Pogacar] is really strong. We're here with [Australian Ben] O'Connor for the GC, we've won two stages, and we've got nothing to lose at all. We'll give it a try tomorrow.
