Second in the Giro d'Italia this spring, and consistently amongst the best in the Vuelta, Chaves was knocked out of the provisional podium down to fourth overall after Alberto Contador (Tinkoff) turned in a strong time trial performance on Friday.
However, on Saturday Chaves launched an ambitious long-distance attack over the Tudons climb, the second last climb, and thanks to clever strategic planning from the Australian squad was able to gain a large amount support from teammate Damien Howson, pulled back from the break, for the long descent from the Tudons and then on the lower slopes of the Aitana itself.
Chaves' move which had marked similarities to that of teammate Simon Yates on the Marie Blanque and then, supported by his teammates, continued through the Aubisque last Saturday, but Contador, the most affected by the manoeuvre, seemed helpless to stop Chaves opening the gap despite a spell of assistance from teammate Yuri Trofimov. Later Contador said he should have tried to follow Chaves directly, but failed to do so.
Over two minutes ahead of the chasing group of favourites at one point, almost enough to begin to trouble Chris Froome and Sky, Chaves finally moved into third overall after gaining 1 minute and 24 seconds on Contador and a ninth place on the stage. That will be enough to net him third overall by 13 seconds in Madrid on Sunday.
"I've confirmed what I already showed to be possible in the Vuelta last year," Chaves, fifth last September as well as the winner of two stages and a first week leader, said afterwards. "That's when I felt up to fighting with the best gc specialists and I hope to continue in the same direction in 2017."
He acknowledged the hard work by Howson as vital to his effort by saying it was "typical of the team spirit in Orica-BikeExchange."
"It was a textbook attack, one which worked out perfectly. And after getting second in the Giro d'Italia, third in the Vuelta is a really important achievement too.
"My whole life I'd dreamed of making an epic attack like the one I did today, and I've finally done it.
"All my family is here, too, and my father was running alongside supporting me at less than three kilometres to go. I've done five Grand Tours, and in two of them I've been on the podium. I've very satisfied about that."
Orica-BikeExchange have had one of their best Vueltas to date, with a podium finish, three stage wins and Simon Yates in sixth place overall.
One consequence of Chaves return to third place overall is that when the race finishes on Sunday, Spain will not have any riders in the Vuelta's top three for the first time since 1996, when Alex Zülle won the race ahead of Swiss compatriots Laurent Dufaux and Tony Rominger and for only the fifth time since cycling's third Grand Tour began back in 1935.