The Ecuadorian, who stormed to a surprise victory in Italy earlier this year, will first have to establish himself as team leader with former winners Nairo Quintana and Alejandro Valverde also named in a strong eight-man team.
It will likely be the 26-year-old's final outing for Movistar before joining Team Ineos in 2020.
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Primoz Roglic and Steven Kruijswijk (both Jumbo-Visma) and Miguel Angel Lopez (Astana) are among Movistar’s rivals in GC.
Defending champion Simon Yates will not defend his title, with Mitchelton-Scott opting for Esteban Chaves as their protected rider.
La Vuelta, available to watch LIVE on Eurosport and Eurosport Player, runs from August 24 to September 15.
Full Movistar team
- Alejandro Valverde
- Nairo Quintana
- Richard Carapaz
- Marc Soler
- Imanol Erviti
- Nelson Oliveira
- Jorge Arcas
- Antonio Pedrero.