The race will be Valverde's first grand tour since returning to action from a two-year suspension for his part in the Operation Puerto blood doping scandal.
His was the standout name as the Spanish team revealed their nine-man line-up for the Tour, which starts on Saturday with a prologue in the Belgian city of Liege.
There was no place for Francisco Ventoso, the recently-crowned Spanish road champion, in a clear indication Movistar have picked Valverde with a view to a high-placed GC finish in Paris.
Valverde has showed some promising signs so far this season, finishing second on the Tour Down Under in January, and Movistar sporting director Eusebio Unzue believes his star man can deliver in France.
"Last year we went for stage victories, but this season, having Alejandro we must be more ambitious, we've got a team full of all-rounders," Unzue said.
"Despite having spent three years without riding a GT, he's in great condition to be our leader and we're convinced he can fight for a podium place.
"Apart from Alejandro, we have strong riders like Cobo, back in a grand tour after winning the Vuelta (in 2011) and into a race he really loves.
"I think he's coming in good form, I expect him to ride a good Tour and build to defend his title in the Vuelta later this year. Also, riders like Costa or Rojas, who are progressing every single year and gaining importance inside the squad."
Movistar roster: Alejandro Valverde, Juan Jose Cobo, José Joaquín Rojas, Rubén Plaza, Vasil Kiryienka, Iván Gutiérrez, Imanol Erviti, Vladimir Karpets and Rui Costa.