Having chanced his arm on ascent of the Col de Peyresourde, Froome still had the lead group with him but, rather than bide his time, the two-time champion opted for a different approach.
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Crouched on top of his handlebars for extra aerodynamics, he opened a 20-second lead and used his time trial qualities to post a sixth career stage win in the Tour.
Orica-BikeExchange rider Adam Yates finished the stage second overall after riding most of the stage as virtual yellow jersey before Froome launched his raid. Ireland’s Dan Martin won the sprint for second from Joaquim Rodriguez of Spain.
“I thought over the top let me just give it a go and see what I can do on the descent – I’ll see if I can catch someone out”, said Froome. “The guys rode all day today so I felt like I owed something to them to really give it my all for the stage”.
It was a fifth stage win in eight for Britons following three for Mark Cavendish and Steve Cummings on Friday.
But once the climb of the monstrous Tourmalet began – the first of four categorised climbs – Frenchman Thibaut Pinot and Rafal Majka of Poland finally got away before German time-trialler Tony Martin breached up to the two climbers. American Tejay Van Garderen will be one of the riders who will try to stay with Quintana and Froome.
With all the favorites still together in the main pack, Team Sky riders Mikel Nieve and Geraint Thomas spent long spells at the front and led the peloton in the fast downhill where Wilco Kelderman crashed on a hairpin alongside his Lotto-Jumbo teammate George Bennett.
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The leading trio were brought back 43km from the end, on the penultimate climb as Quintana’s Movistar and Sky took turns setting a fierce tempo at the front of the peloton.
