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Dainese came from a good position behind to overtake Filippo Ganna (Ineos Grenadiers) in the sprint to the line with Merijn van den Berg (EF Education-Easypost) taking third.
The bunch had been disrupted just outside the final kilometre by a crash that took down points classification leader Kaden Groves (Alpecin-Deceuninck), with the Australian somehow managing to land on his feet as a number of his teammates and other riders came down.
The crash appeared to be caused by an overlap of wheels with EF Education-EasyPost's lead-out rider and a Alpecin-Deceuninck rider, who came down first at high speed and bring down about 10 other riders.
Nonetheless, it was another Grand Tour stage win for Dainese, his third of the season after two at the Giro d’Italia.
"It's really nice for sure," said Dainese. "We did a super job. We were looking at the sprints in the first two weeks and what we did wrong there. Today we executed the plan 100%.
"I think was really unlucky to lose a couple of guys in the crash but to that point, I was in a perfect position where I wanted to be. And it was a bit headwind so Ganna and the other guys just went a bit early and then I was waiting for my moment to go in the wind. I am super happy to finish a hard Vuelta in this way."
Dainese will shift squads over to Tudor Pro Cycling team next season, the change meaning that the Italian wanted to farewell his current team in style.
"Obviously this feels special because of that," said Dainese. "Today I've had a lot of pressure because I knew there was kind of the last opportunity for a sprint. Then I really want to say thanks to the team. They did a good job."
La Vuelta continues with stage 20, a hilly stage that will offer the final opportunity for a major change on the general classification. Watch from 7:45pm AEST on SBS On Demand, with the broadcast on SBS VICELAND from 8.30pm AEST.
