Belgian Jelle Vanendert took the 168.5km mountainous trek from St Gaudens to Plateau de Beille to claim victory in the 14th stage of the Tour de France - his maiden win.
Spain's Samuel Sanchez finished second behind the Omega Pharma-Lotto rider and Luxembourg's Andy Schleck was third.
France's Thomas Voeckler retained the overall leader's yellow jersey.
Voeckler had been expected to lose his lead on Saturday, but held onto his one minute, 49 second advantage.
"I would be lying if I said I expected to be with the best climbers today," admitted Voeckler.
"I thought I had a chance to keep the jersey, but I was really surprised to be up there with them. But it was a good surprise."
Sanchez (Euskaltel-Euskadi) finished 21 seconds behind, with Andy Schleck (Leopard Trek) leading the group of favourites home, 46 seconds adrift.
Andy Schleck finished two seconds ahead of Cadel Evans (BMC Racing), Rigoberto Uran (Team Sky), Alberto Contador (Saxo Bank-SunGard), Voeckler and Frank Schleck, who were all 48 seconds adrift of Vanendert.
On four previous occasions when a stage has finished at Plateau de Beille, the winner has gone on to stand on top of the podium in Paris.
However, with seven days of racing and the Alps to come, it is premature to announce Vanendert as a successor to Marco Pantani (1998), Lance Armstrong (2002 and 2004) and Alberto Contador (2007) - particularly due to his already-hefty deficit.
With six classified climbs, including the 15.8km ascent to the finish, it was always likely to be a day for the general classification contenders, including Contador, racing with a large support who had flooded over the Spanish border.
But, as on Thursday's 12th stage to Luz-Ardiden, defending champion Contador appeared short of his best and remained four minutes behind Voeckler.
Sunday's 193km 15th stage from Limoux to Montpellier is likely to end in a sprint finish, where green jersey holder Mark Cavendish (HTC-Highroad) comes into his own, giving the general classification hopefuls time to gather breath before the Alps.
STAGE 14 RESULT
1. Jelle Vanendert (Belgium/Omega Pharma-Lotto) 5h 13m 25s
2. Samuel Sanchez (Spain / Euskaltel) +21"
3. Andy Schleck (Luxembourg / Leopard) +46"
4. Cadel Evans (Australia / BMC Racing) +48"
5. Rigoberto Uran (Colombia / Team Sky)
6. Alberto Contador (Spain / Saxo Bank)
7. Thomas Voeckler (France / Europcar)
8. Fraenk Schleck (Luxembourg / Leopard)
9. Jean Christophe Peraud (France / AG2R)
10. Pierre Rolland (France / Europcar)
11. Ivan Basso (Italy / Liquigas)
1. Thomas Voeckler (France/Europcar) 61hrs 04mins 10secs
2. Fraenk Schleck (Luxembourg / Leopard) +1:49"
3. Cadel Evans (Australia / BMC Racing) +2:06"
4. Andy Schleck (Luxembourg / Leopard) +2:15"
5. Ivan Basso (Italy / Liquigas) +3:16"
6. Samuel Sanchez (Spain / Euskaltel) +3:44"
7. Alberto Contador (Spain / Saxo Bank) +4:00"
8. Damiano Cunego (Italy / Lampre) +4:01"
9. Tom Danielson (U.S. / Garmin) +5:46"
10. Kevin De Weert (Belgium / Quick-Step) +6:18"