Hindley leads Vingegaard with the Dane pulling off a major coup on the final mountain and now has a 53-second advantage on Pogacar in the overall standings, which took a major shake up.
Bora-Hansgrohe rider Hindley, the 2022 Giro d'Italia winner, shook off his rivals on the Col de Marie-Blanc to break clear in the yellow jersey standings.
The 27-year-old finished 32 seconds ahead of Italy's Giulio Ciccone and Austrian Felix Gall with Vingegaard fifth at 34sec. Ciccone climbed to third in the overall with his second place. "I'm here for the overall win and the aim was to put as much time as possible into the others," said Hindley. "It has been a dream since I was six years old but I never thought I'd find myself in the yellow jersey," he said. "It was chaotic behind with different teams riding with various aims.
I got the in and the lead so I'm delighted, it's going to be a crazy bike race." Vingegaard's Jumbo-Visma stunned the UAE Team when Wout Van Aert dropped back from an early break and led Vingegaard uphill with an impressive 500m pull.