Team Sky has won the opening time trial, making Peter Kennaugh the race leader after the first stage of the Tour of Spain, while Australia's Orica Bikeexchange finished third.
In the 27.8-km ride from Ourense to Castrelo de Mino, the British rider guided his team across the finish line in 30 minutes 37 seconds.
It was a thrilling end with home team Movistar, led by Spaniard Alejandro Valverde, 4/100ths of a second adrift.
Orica Bikeexchange were third and BMC Racing of the United States, the world champions, finished fourth.
It was a good start for Sky's Chris Froome, bronze medallist at the Olympic time trial in Rio who is looking for a rare Tour de France-Vuelta double.
Alberto Contador, back in action after withdrawing from the Tour de France due to injury, endured a difficult afternoon with his Tinkoff team ending up 52 seconds off the pace.
The Spaniard, a triple Vuelta winner, did not take part in the event last year.
"It's a big deficit," Contador told reporters. "Better days will come.
"There are still 20 stages to go and we will try to reduce the gap day by day."
Last year's Vuelta winner Fabio Aru is not contesting the 2016 race.
The 27-year-old Kennaugh will wear the red jersey in Sunday's second stage, a 160.8-km ride from Ourense to Baiona.
