The Colombian of team Movistar showed himself to be the best climber and with the most cunning, taking time on Froome and his other rivals when they did not expected on the stage to Formigal.
The 2016 season shines brighter for Quintana now after struggling to achieve third and failing to challenge Froome in the Tour.
"It helps get over what happened in the Tour," 26-year-old Quintana said in the Vuelta's red jersey.
"It wasn't a failure. I'm still learning a lot. It was a very tough race this year and I have to go on learning."
Quintana was billed as Froome's only direct rival ahead of the Tour de France after twice finishing second overall. He was not at his best and Froome, without a serious challenger, had an easier ride to his third title. Instead of fighting for the win, Quintana fought to take third overall by Paris.
The five-foot-five, 121-pound cyclist returned home to Boyacá, in the East Andes, for rest and training. He arrived for the Vuelta a España a new man, whereas Froome arrived after a tough schedule of criteriums, RideLondon and the Olympics. It produced a prefect head-to-head battle and a chance for Quintana's revenge.
"This Vuelta win means a whole lot to me. At the Tour, I reached the podium more out of class rather than legs. I didn't feel well in France, yet I found my best condition here," added Quintana.
"Also, it was a race with almost all the big GC names in the peloton present: a huge Chris Froome; Alberto Contador, who is one you must always keep an eye on; Chaves and Orica... Winning the race this way, and against them, makes it even more valuable."
Quintana became the most accomplished Colombian grand tour rider with his win. He was the first to win the Giro d'Italia in 2014 and became the second after Luis Herrera in 1987 to win the Vuelta a España title. All that he needs to make a complete set is the Tour.
"It's very hard," Quintana said. "Sky keeps Froome well protected, but Movistar will try to take advantage of any situation. This win in the Vuelta, though, has given us the added confidence to try to win it."
Movistar, which has a big market in Colombia, will make sure Quintana has support to race for a Tour win. Today, at a press conference in Madrid, the telecommunications company renewed its sponsorship contract for three more years, through 2019, with the Spanish team.
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