With the last remnants of the early breakaway caught midway up the final climb of the day, it was all left to play for amongst the big contenders as the roads tilted steeply upwards.
Esteban Chaves (Orica-BikeExchange) was the first to attack, with two kilometres left to race. He quickly established an advantage and going under the flame rouge with 15 seconds advantage it looked like there might be a stage win in the offing for the Colombian rider.
However, an acceleration from Valverde, followed by scintillating attacks from Quintana and then Froome quickly saw the front of race catch up to the Orica-BikeExchange rider, leaving him to struggle on to the finish.
Froome and Quintana were trading haymakers up front as Alberto Contador (Tinkoff) fought to get on terms with the pair, not quite managing it and fading back to the second group with Valverde and Leopold Konig (Team Sky).
The leading duo watched each other as the climb flattened out nearer the top and on the final dash to the line it was Froome who unleashed his superior sprint to take the win, punching the air as he crossed the line.
Alejandro Valverde rallied to slip into third on the stage, six seconds back, but gave up his second overall to Froome, who nows sits 54 seconds adrift of Quintana in the fight for the red jersey.
The victory mirrored his first Grand Tour stage win back in 2011, where he was also the winner up the Pena Cabarga and sat second overall at that point also.
"I’ve got some special memories from 2011 here. To add to that here is an incredible feeling,” said Froome.
“Quintana is really strong at the moment. He has the leader’s jersey and I’m just trying to do as much as I can day by day to get closer to him.
“I want as much time as I can get, he wants as much time as he can get and that makes the race exciting.”
"I just want to thank my team-mates for all the hard work they've done and also my family at home, for all the motivation and support, because at this point in the season after all the work I've done, it's really tough for me at the moment. A big thank you to them. I'm looking forward to coming home soon."
As it happened
Several riders posed for photos with dinosaurs before the race heading off from Museo Jurasica on the 168.6 kilometre stage to Pena Cabarga. There were two non-starters after Tuesday's rest day, with Silvio Herklotz (Bora-Argon18) and Simon Clarke (Cannondale-Drapac) withdrawn after falls on Stage 10.
Clarke rode up Lagos de Covadonga one-handed after crashing on Monday, but was later diagnosed with a dislocated shoulder and possible damage around the AC joint and instead headed to Barcelona for surgery.
Soon after the start his Cannondale-Drapac team-mate and last year’s National Road Series champion, Patrick Bevin, also dropped out. The New Zealander had also crashed on Stage 10, unfortunately onto an already injured hand.
The pace was high from the start and breakaways were unable to get any leeway with the near 50km/hr average speed in the opening hour.
A sizeable move final eventually got away and was given some freedom after the 50 kilometre mark. The gap between the 23-man break and the peloton stretched out to five minutes mid-stage and it was left for a combination of Movistar and Tinkoff to do the pace-making, with Orica-BikeExchange and Team Sky also attentive to the front of the race.
Coming into the flat run before the climb, the escapees were in sight and the catch was inevitable with the big teams jockeying to get their leaders in good position for the final ascent. Ruben Fernandez (Movistar) did another stellar job on the early slopes of the climb to shed most of the field, once again confirming his status as an elite climber within the peloton.
With the gradient steepening with two kilometres left to go, Chaves bravely threw out a bold attack. He quickly opened a 15-second gap and looked to be heading to victory but first Valverde picked up the chase and then Quintana surged away in pursuit, producing several severe accelerations to try to distance Froome from his wheel.
However the three-time Tour champion stayed in Quintana’s wheel and was able to make his own attack to prove a point, as their rivals suffered behind.
At the finish it was Froome who saluted, but with the pair so apparently evenly matched on the climbs at the moment, it shapes to be a fascinating battle for the red jersey all the way to Madrid.
Second place on the day, but still the overall leader, Nairo Quintana was a bit perplexed with Froome's approach after the finish.
"Froome’s tactics today? It’s difficult to think about how he rides. He’s a man who plays different approaches, and gets different or similar results.
"Last Saturday, at another short climb like La Camperona, I put time on him, and today, into similar terrain, we came together across the finish.
"We’ll see how the two of us react on longer climbs, into longer stages. We’ve also got our strategy, but we must remain cautious about him: he’s probably the one to beat.”
“We crossed the finish line together with Froome today, though he won the stage as he’s usually faster in sprints. I keep in mind from today’s that Chris is showing to be strong, probably the biggest threat GC-wise - we must keep focus and look for other demanding stages, like Aubisque or Formigal, where we will surely see some fireworks."