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Pogacar was the only rider to follow Vingegaard when the Dane attacked on the Col du Tourmalet, and the two marked each other until the Slovenian surged on the final climb of the day to go solo and win his 10th Tour de France stage by 24 seconds over his rival.
The performance was payback from Pogacar after being distanced by the 2022 champion on yesterday's stage to Laruns, as the Slovenian came into the day 53 seconds behind Vingegaard with a point to prove.
Australian Jai Hindley (BORA-Hansgrohe) dropped to third in the general classification after he was left behind when Jumbo-Visma and Vingegaard shredded the peloton on the Tourmalet, relinquishing the yellow jersey to the Dane who now leads Pogacar by 25 seconds.
"It's sweet to win today and take some time back," Pogacar said following the stage. "I feel a little relieved and much better.
"I was thinking when they [Jumbo-Visma] started pulling on the Tourmalet, if it's going to go like yesterday we can pack our bags and go home, but luckily I had good legs and could follow quite comfortably.
"When I felt it was the right moment at the end I attacked, and it was a big relief."
While Vingegaard now has the race lead despite the effort, the gap to second is a much more manageable one for Pogacar with two weeks of racing still to go, predicting a big fight until the end.
"I'd say now the gap is almost perfect, and it's going to be a big, big battle until the last stage I think."
Jumbo-Visma pulled out all the stops to try to isolate and distance Pogacar, starting with super domestique Wout van Aert who attacked right from the start of the stage to form the day's breakaway that included the likes of Mathieu van der Poel (Alpecin-Deceuninck) and Julian Alaphilippe (Soudal-QuickStep).
Van Aert led the break and turned up the pace onto the Tourmalet as his teammates did the same on the peloton behind, gradually dropping rider after rider until Hindley and Pogacar were the only ones hanging on, the Australian yellow jersey dropping when Sepp Kuss took over.
Vingegaard launched shortly before the top of the Tourmalet, Pogacar looking better than yesterday as he stuck to the Dane's wheel and the pair swiftly set off up the road, putting two minutes into the group of contenders behind including the yellow jersey.
They continued to mark each other until they reached van Aert, who began pulling after dropping back from the breakaway and with the Dutchman on the front the race favourites quickly caught the leading group before the final climb of the day.
Van Aert's gargantuan effort took Vingegaard and Pogacar all the way to the six kilometre to go mark on the stage, when the Dane attacked, but his Slovenian rival was again equal to it and unleashed a move of his own two kilometres later that proved decisive.