Basque rider Mikel Nieve, who won a stage at the race in 2010, will be the primary support rider for Chaves, along with Damien Howson, while Slovenian sprinter Luka Mezgec comes to the race in strong form having won two stages at the Tour de Pologne.
Reigning champion Simon Yates was rumoured to be considering a return to the race, what would have been his third Grand Tour of the season, but has not been included in Mitchelton-Scott's lineup.
Chaves was forced to miss last year's edition of the race after struggling with mononucleosis through the second half of 2018. Chaves returned to racing in February, building his way up to the Giro d'Italia, where he took a stage win at San Martino di Castrozza.
This year, the Vuelta features a grand total of 12 uphill finishes, including eight stages with mountaintop finishes. That, in addition to the lumpy 36km time trial across the border in France, means it's a parcours suited to the Colombian's abilities.
"I feel happy, I feel ready," said Chaves in a team release. "The course is really good for riders like me. Normally the Vuelta suits me really well. I like the heat and I am happy with the preparation I had in Colombia.
"We have a really nice group. [Mikel] Nieve is for sure in good shape. Also we saw the guys at the Tour de Pologne, like Luka Mezgec. He was sprinting really fast. The sprints in the Vuelta are a bit different and I think they are good for him.
"I'm excited to start racing. Hopefully for all the work we have put in, the Vuelta will be good and that is what excites me."
As well as Nieve, Howson and Mezgec, the Australian team will bring Tsgabu Grmay, Nick Schultz, Sam Bewley and Dion Smith to Spain. It all adds up to a team ready to work for Chaves, who will target the GC at the race. He finished third overall at the Vuelta back in 2016.
"The GC is an objective for us and we have Esteban Chaves for that," said directeur sportif Julian Dean. "As well as that we are focussing on stage wins.
"If you look at the race across the three weeks, it is really relentless and already within the first week there's some real aggressive and hard stages. It's going to be a race where strength and vigilance is going to be necessary from anyone who is hoping to contest the overall."
Mitchelton-Scott for the Vuelta a España (August 24-September 15): Sam Bewley (NZl), Esteban Chaves (Col), Tsgabu Grmay (Eth), Damien Howson (Aus), Luka Mezgec (Slo), Mikel Nieve (Spa), Nick Schultz (Aus), Dion Smith (NZl).