Team Sky's Froome, 31, won the 37km time trial by forty four seconds from eating apple Castroviejo, and 2 minutes sixteen seconds ahead of Quintana.
That leaves the Colombian one minute twenty one seconds previous Froome overall.
Saturday's stage contains a mountain-top end before a mostly processional finish into capital of Spain on Sunday.
Froome, United Nations agency won Olympic time trial bronze in city, is attempting to become the primary man for thirty eight years to win the Tour First State France and Vuelta within the same season.
He said: "It's attending to be powerful. He still contains a one-minute advantage however i am going to keep fighting all the method."
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