Valverde’s effort puts him back in the overall race lead, 15 seconds ahead of team-mate Nairo Quintana (Movistar) and 18 seconds ahead of Contador. Froome is now fourth at 22 seconds.
After spending time in an ill-fated break on the previous day’s stage, Pim Ligthart (Lotto-Belisol) joined forces with Lluis Mas (Caja Rural) on stage six to create the day’s escape. With no threat to the general classification, the duo were allowed to build up a large advantage over the peloton, reaching over 14 minutes before hitting the first of three categorised climbs.
Mas had interest in increasing his lead in the King of the Mountains classification, and Ligthart looked happy to play along, with the Caja Rural man crossing the line first over the second category Alto de Zafarraya and third category Alto de los Bermejales.
Within the final 40km, Katusha and Garmin-Sharp looked active at the front of the peloton, upping the pace and steadily chipping the break’s advantage away.
Orica-GreenEdge then took over the pace-setting to whittle down the break’s advantage to under 30 seconds by the base of the final ascent to the line at La Zubia. Ligthart had one last solo effort as Mas dropped back but was caught with three kilometres to go.
At this point, the peloton had been whittled down to a select number of riders as the climb’s gradient hit double figures. Valverde upped the pace with Movistar team-mate Quintana with two kilometres to go, to further reduce the pack as the likes of Cadel Evans (BMC), Wilco Kelderman (Belkin) and Adam Yates (Orica-GreenEdge) slipped back.
Joaquim Rodriguez (Katusha) was the first to launch an attack, followed by Valverde. Froome then ground out a steady pace to bridge up to them, dragging Contador and Quintana with him. Froome briefly led, but Valverde came around him to take the victory.
Garmin-Sharp’s hopes of a decent overall placing were once again dashed with Daniel Martin finishing 18th on the stage and losing 59 seconds to Valverde. Yates finished two places back in 20th and at 1-07.
Friday’s seventh stage from Alhendin to Alcaudete is another lumpy day, but with less of an ascent to the line.
Vuelta a Espana 2014, stage six: Benalmádena to La Zubia, 167.1km
1. Alejandro Valverde (Spa) Movistar in 4-35-27
2. Chris Froome (GBr) Sky
3. Alberto Contador (Spa) Tinkoff-Saxo at same time
4. Joaquim Rodriguez (Spa) Katusha at 8 secs
5. Nairo Quintana (Col) Movistar at 12 secs
6. Fabio Aru (Ita) Astana at 18 secs
7. Esteban Chaves (Col) Orica-GreenEdge at 25 secs
8. Daniel Navarro (Spa) Cofidis at same time
9. Mikel Nieve (Spa) Sky at 32 secs
10. Robert Gesink (Ned) Belkin at 33 secs
20. Adam Yates (GBr) Orica-GreenEdge at 1-07
Overall classification after stage six
1. Alejandro Valverde (Spa) Movistar in 22-48-08
2. Nairo Quintana (Col) Movistar at 15 secs
3. Alberto Contador (Spa) Tinkoff-Saxo at 18 secs
4. Chris Froome (GBr) Sky at 22 secs
5. Esteban Chaves (Col) Orica-GreenEdge at 41 secs
6. Joaquim Rodriguez (Spa) Katusha at 45 secs
7. Robert Gesink (Ned) Belkin at 55 secs
8. Fabio Aru (Ita) Astana at 58 secs
9. Warren Barguil (Fra) Giant-Shimano at 1-02
10. Wilco Kelderman (Ned) Belkin at 1-06
17. Daniel Martin (Irl) Garmin-Sharp at 1-37
67. Adam Yates (GBr) Orica-GreenEdge at 19-15
Stage five win for German sprinter John Degenkolb at the Vuelta a Espana; Michael Matthews retains overall lead