Winner Anacona (Lampre-Merida) soloed to victory on the summit finish at Valdelinares as Nairo Quintana (Movistar) took the red jersey on stage nine.
The Colombian, 26, who was third at the Tour of Utah, was the last remaining survivor from a large break which went clear after 25km of racing.
Having lost time in the echelons on stage eight, Anacona started the stage 2’50” down on red jersey Alejandro Valverde (Movistar) but after pressing on alone with six kilometres to race, he is firmly back in the race for the red jersey.
Anacona was one of 31 riders to earn a gap after 25 kilometres, with some strong riders going up the road – including Giro d’Italia King of the Mountains winner Julian Arredondo (Trek Factory Racing), Dario Cataldo (Team Sky), Damiano Cunego (Lampre-Merida) and Ryder Hesjedal (Garmin-Sharp) also making the split.
Bon Jungels (Trek Factory Racing), Tom Boonen (Omega Pharma-Quickstep) and Adam Hansen (Lotto-Belisol) also went up the road, alongside King of the Mountains leader Lluis Guillermo Mas (Caja Rural).
Anacona, the best-placed rider in the break, was virtual leader for quite some time as the group’s lead peaked at eight-and-a-half minutes.
Though the bunch had worked to bring them back, and Javi Moreno (Movistar) worked hard to stay with the front group and stop their advantage impacting on the red jersey, Anacona was still well placed as the ascent to Valdelinares began.
With just Anacona, Jungels and Moreno remaining from the original break, which had broked up after a series of accelerations over the climbs, the trio held a four-minute lead over the red jersey group as the climb began.
That advantage was soon whittled down, however, as a race within a race ensued further back – the GC men looking to steal seconds from each other as Tony Martin (Omega Pharma-Quickstep) ramped the pace up.
Up the road, Anacona pressed on alone as the advantage tumbled – quickly earning a bug gap as Moreno and Jungels were caught by some of their former breakaway companions – Cunego among them.
Within what remained of the peloton, Chris Froome (Team Sky) sat with his team-mates on the front, looking well placed to attack.
The injection of pace which began to split the group up, however, came instead from Garmin-Sharp’s Dan Martin, with three kilometres remaining.
The attack led to the bunch becoming strung out behind him, and the counter-attacks quickly started – Alberto Contador (Tinkoff-Saxo) accelerating with two kilometres to go as Valverde and Froome found themselves losing position.
Contador quickly earned a ten-second gap on his rivals, but Katusha rallied for Joaquim Rodriguez as Eduard Vorganov and Dani Moreno chased him down – Quintana latching onto the chase behind them.
Anacona was first across the finishing line, some 45 seconds clear of his nearest challenger, Alexey Lutsenko (Astana), to celebrate his first professional victory, on one of the biggest stages of all.
The action was just beginning further back, however, with Froome and leader Valverde now having missed both Contador’s attack and Rodriguez’s counter-move.
Contador eventually crossed the line in 12th place, 2’16” after Anacona, with Rogriguez and Quintana catching his wheel to share his time.
All eyes consequently turned to the clock, with another 23 seconds having ticked over by the time Valverde, Froome, Fabio Aru (Astana), Rigoberto Uran (Omega Pharma-Quickstep) and Martin reached the summit.
It left the Colombian fans celebrating a double success, with Anacona’s stage win and surge up the general classification and now Giro d’Italia champion Quintana pulling on the red jumper for the first time.
Just nine seconds now separates the two countrymen, with Contador and Valverde in between and Froome and Rodriguez also within 30 seconds of the lead as the peloton takes in the first rest day of this year’s race.
Vuelta a Espana 2014: stage nine – report
1) Winner Anacona (COL) – Lampre-Merida – 4.34.14hrs
2) Alexey Lutsenko (KAZ) – Astana +45”
3) Damiano Cunego (ITA) – Lampre-Merida +50”
4) Javier Moreno (ESP) – Movistar +1.04
5) Pello Bilbao (ESP) – Caja Rural +1.12
6) Jerome Coppel (FRA) – Cofidis +1.21
7) Ryder Hesjedal (CAN) – Garmin-Sharp +1.33
8) Adam Hansen (AUS) – Lotto-Belisol +1.45
9) Bob Jungels (LUX) – Trek Factory Racing +1.49
10) Fabio Felline (ITA) – Trek Factory Racing +2.08
1) Nairo Quintana (COL) – Movistar +35.58.05hrs
2) Alberto Contador (ESP) – Tinkoff-Saxo +3”
3) Alejandro Valverde (ESP) – Movistar +8”
4) Winner Anacona (COL) – Lampre-Merida +9”
5) Chris Froome (GBR) – Team Sky +28”
6) Joaquim Rodriguez (ESP) – Katusha +30”
7) Fabio Aru (ITA) – Astana +1.06
8) Robert Gesink (NED) – Belkin Pro Cycling +1.19
9) Rigoberto Uran (COL) – Omega Pharma-Quickstep +1.26
10) Warren Barguil (FRA) – Giant-Shimano – ST