The Alpecin-Deceuninck rider showed grit and determination in tricky conditions to win the 187-kilometre mountain stage in 4hr 38min after suffering an early puncture in the race.

Evenepoel of Quick-Step Alpha Vinyl finished 15 seconds behind Vine at the summit of the Ascensión al Pico Jano to replace Frenchman Rudy Molard of Groupama-FDJ at the top of the general classification standings.

Spanish duo Enric Mas of Movistar Team and Juan Ayuso of UAE Team Emirates came third and fourth respectively, while Slovenia's defending champion Primož Roglič of Jumbo-Visma was part of an 11-strong group that trailed Vine by 1:37.

"It is almost unreal," said Vine who claimed his first Grand Tour stage victory.

"There were so many [kilometres] to go, I missed the break, I got a flat tire in the first 5km.

"And even though it was still the team's plan if it came back together for me to go on the final climb, it was unreal to be able to do that.

"And to do that from the general classification group is incredible.

"I have been working towards this all year after last year, coming so close.

"It is a dream come true."

Evenepoel holds a 21-second lead over Molard in the general classification.

"I’m proud to be leader," said Evenepoel.

"This is the reason why I’ve been working so hard for so long.

"What I showed today is maybe one of the best things I did on a bike.

"In an uphill finish to put such a strong performance thanks to the team is a dream come true."

Competition is due to continue tomorrow with riders tackling a 190.1km route from Camargo to Cistierna.