Quintana will be looking to make up for the relative disappointment of the Tour de France. Despite finishing third on the overall podium, the Colombian was unable to challenge the dominance of Chris Froome (Team Sky) and struggled to set himself apart from the other GC contenders.
Froome and Alberto Contador (Tinkoff) have already confirmed their attendance at the final three-week race of the year, so the Movistar riders will need to be on their best form if they are to challenge for the final podium on Sunday September 11.
Taking the line on Saturday August 20, this will be Valverde's fifth consecutive Grand Tour. Already this season the veteran Spaniard has finished third in the Giro d'Italia and sixth in the Tour.
All the latest ahead of the 2016 Vuelta a España
The 36-year-old is aiming to become only the third rider in history to gain a top-ten finish in all three Grand Tours in the same season.
Quintana came second in the 2015 Tour de France with Valverde one step down in third. Both riders then rode last year's Vuelta, and came fourth and seventh respectively; placings they will be looking to better this year.
The 2015 result is the younger rider's best performance in the Vuelta. He was one of the favourites for overall victory in 2014 but crashed out on stage 11.
Valverde won the 2009 edition of the race and has came second twice and third a further three times since he first appeared in the race in 2002.
Movistar line-up, 2016 Vuelta a España
Jonathan Castroviejo (Esp)
Imanol Erviti (Esp)
Ruben Fernandez (Esp)
José Herrada (Esp)
Dani Moreno (Esp)
Nairo Quintana (Col)
José Joaquin Rojas (Esp)
Rory Sutherland (Aus)
Alejandro Valverde (Esp)
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