With the final stage a processional affair into Madrid - the top 10 will hold their present GC positions - Saxo Bank rider Contador managed to keep a lead of 1:16 from Movistar's Valverde and 1:37 from Katusha's Rodriguez.
El Pistolero looked to be in serious trouble on the final ramps of the mountain-top finish but measured his efforts to keep the pair at bay on GC.
The stage was won by Denis Menchov (Katusha) who, after being part of the early breakaway, rode away from fellow breakaway rider Richie Porte (Sky) to take the stage win some four minutes ahead of the GC contenders.
On the penultimate stage, the riders were faced with three Category 1 climbs, a Category 2 climb and a finish on the HC Bola del Mundo - and the break of the day held on from 20km right up until the finish line.
The early break consisted of over 20 riders including Porte, Menchov, Kevin De Weert (Omega Pharma Quick Step), Gert Steegmans (OPQS), Zdenek Stybar (OPQS), Klaas Lodewyck (BMC), Maxime Bouet (AG2R), Simon Geschke (Argos Shimano), Juan Jose Cobo (Movistar), Matteo Montaguti (AG2R), Leonardo Duque (Cofidis), David de la fuente (Caja Rural), Frederik Kessiakoff (Astana), Tiago Machado (Radioshack Nissan), Kevin Seeldrayers (Astana), Tom Peterson (Garmin Sharp), Romain Sicard (Euskaltel), Denys Kostyuk (Lampre), Eros Capecchi (Liquigas) and Daniel Navarro (Saxo Tinkoff) - and the bunch were quite happy to allow them to contend for points on top of the first four climbs of the day.
Mountains classification leader Simon Clarke (Orica GreenEdge) was also in the group and his efforts over the first three climbs were enough for him to secure victory and hold the jersey into Madrid.
It was at this point that Euskaltel-Euskadi began to chase hard on the front of the main bunch. And while they did whittle down the gap from over 10 minutes at one point, it did not come down as quickly as they would have liked.
The breakaway still held an advantage of 6'40” going over the top of the Category 1 Puerto de Cotos, the penultimate climb of the day, but the leaders were working well together and were not willing to be reeled back in.
With 15km to race, and fast approaching the foot of the Bola del Mundo, the peloton was still over five minutes back and it was obvious that the winner would come from the breakaway. As the climb began, riders immediately began to fall off the back of the leading group and it was here that the attacks began.
Capecchi, Bouet and De Weert launched themselves off the front and were quickly followed by Porte, Menchov and Kessiakoff. A counter-attack by Porte and Menchov cut this group from six to three and this is how it would stay until the 3km mark when a clearly struggling De Weert fell behind.
Porte and Menchov traded turns at the front over the gruelling ramps of between 11% and 23% on the way up to the finish, but neither had the energy to break the other and it wasn't until 150m from the finish line that the Russian got the jump on Porte to leave him in his wake and seal the stage victory.
Behind them the red jersey group was becoming every smaller and it was not until they turned off the tarmac road and onto the single track concrete trail that the fireworks began. Contador's Saxo-Tinkoff team took control and drove hard up the first kilometre of the climb and did serious damage to the other GC contenders. Quickly everyone but Rodriguez, his team-mate Moreno and Valverde were left to battle it out.
In a reversal of roles, it was now Rodriguez's turn to launch stinging attacks and after two attempts, the third one stuck. From here Rodriguez pushed his way to the line as Contador and Valverde floundered behind him. The red jersey seemed to be having serious difficulty with the pace of Rodriguez, but he would have been only too aware of the time gap between them.
Contador lost over 20 seconds to Valverde, but retains the race lead and will ride into Madrid tomorrow in the red jersey.