Valverde also won the Fleche Wallonne earlier this month

The Caisse d'Epargne team rider out-sprinted Switzerland's Alexandre and Australia's Cadel Evans at the end of the 127-km mountain stage.

Spaniard Alberto Contador finished in the same time as Valverde and retained the overall race lead.

The Tour ends with a 20.4km individual time trial in Lausanne on Sunday.

Provisional results of Stage Four

1. Alejandro Valverde (Spain / Caisse d'Epargne) 3:41:24"
2. Alexandre Moos (Switzerland / Phonak) same time
3. Cadel Evans (Australia / Davitamon - Lotto) same time
4. Joerg Jaksche (Germany / Liberty Seguros) same time
5. Sylwester Szmyd (Poland / Lampre) same time
6. Oscar Sevilla (Spain / T-Mobile) same time
7. Alberto Contador (Spain / Liberty Seguros) same time
8. Christophe Moreau (France / AG2R) same time
9. Andrea Noe (Italy / Liquigas) same time
10. Sergio Ghisalberti (Italy / Milram)

General classification

1. Alberto Contador (Spain / Liberty Seguros) 16:16:25"
2. Alejandro Valverde (Spain / Caisse d'Epargne) +6"
3. Cadel Evans (Australia / Davitamon - Lotto) +24"
4. Joerg Jaksche (Germany / Liberty Seguros) +28"
5. Sergio Ghisalberti (Italy / Milram) +54"
6. Andrea Noe (Italy / Liquigas) +57"
7. Andrey Kashechkin (Kazakhstan / Liberty Seguros) +1:04"
8. Sylwester Szmyd (Poland / Lampre) +1:07"
9. Alexandre Moos (Switzerland / Phonak) +1:11"
10. Chris Horner (U.S. / Davitamon - Lotto) +1:14"