The 23-year-old, competing in his maiden Grand Tour, escaped with 20 other riders during the 163 kilometres ride from Betanzos to San Andrés de Teixido.

Belgium’s Thomas De Gendt and France’s Pierre Rolland were among the key instigators of the move, which fended off the attentions of the main field throughout the day.

Their advantage grew to over five minutes by the final 25km, with De Gendt, the Czech Republic’s Zdenek Stybar and France’s Axel Domont all making attempt to go solo at the front of the race.

Domont was briefly able to achieve the feat, but was caught and passed by Calmejane on the Alto de Capella climb at 12km to go.

The French rider extended his advantage in the closing kilometres to claim a superb victory, with the first year professional crossing the line in a winning time of 4 hours 05min 19sec.

Colombia’s Darwin Atapuma finished 15 seconds adrift of the stage winner in second, outsprinting the United States’ Ben King.

The BMC Racing rider celebrated moving to the top of the general classification following his display, with the overnight leader Ruben Fernandez of Spain being part of the peloton.

Spain's Alejandro Valverde led the main field across the line, ending more than two minutes after the winner, to move into second place overall.

The Spaniard is 26 seconds down on Atapuma and lies four seconds ahead of Britain’s Chris Froome, seeking to become the first man in 38 years to win the Tour de France and Vuelta a España in the same season.

The Colombian duo of Esteban Chaves and Nairo Quintana are fourth and fifth respectively, 39 seconds off the race lead.

Team Sky won the team trial on the opening stage of the International Cycling Union (UCI) World Tour race on Saturday (August 20), with Belgium’s Gianni Meersman and France’s Alexandre Geniez triumphing on stage two and three respectively.

Stage five is due to see the riders tackle a 171km flat stage from Viveiro to Lugo.