Germany's Matthias Kessler won stage three of Le Tour after long-time leader Jose Luis Arrieta was caught by the peloton just 3km from Valkenburg.
Kessler came close to winning stage two
Belgium's Tom Boonen took over the yellow jersey from Norway's Thor Hushovd after finishing fourth.
T-Mobile's Kessler finished 50m ahead of team-mate Michael Rodgers while Lampre's Daniele Benati was third.
However, favourite Alejandro Valverde is out of the race after crashing and breaking his collarbone.
"Yesterday I had a good feeling but it did not work," said Kessler, who narrowly missed out on victory in stage two.
"Today I was also feeling good so I tried again, and as the final climb was just before the finish I knew I had a better chance to win."
If you defend the yellow jersey it can hurt your chances of keeping the green jersey
Boonen, a sprinter by profession, has no illusions that he will be leading in Paris, but he is savouring wearing the yellow jersey in his native Belgium on Wednesday.
"Maybe that happens only once in ten years, so it's something pretty special," said Boonen, whose lead is all the more remarkable as his bike suffered a puncture 5km from the finish.
Boonen took the points competition green jersey from Australian Robbie McEwen on Tuesday and is now in possession of three jerseys.
But he said he would have to review whether it was worth defending his yellow jersey when that could damage his chances in the points race.
In the general classification, Quick Step's Boonen has a one second lead over Rogers.
"Everybody knows Rogers is not going to sprint for the bonus seconds, he'll be keeping his energy for the time trial (on Saturday)," said Boonen.
"So I will have to look more towards McEwen and Hushovd and see how far they are away from me.
"But if you defend the yellow jersey it can hurt your chances of keeping the green jersey, so we're going to have to look at what our priorities are."
Arrieta, Jens Voigt, Unai Etxebarria, Jose Luis, Christophe Laurent and Jerome Pineau broke away after just 18km in searing heat in Luxembourg.
They led the bunch by up to six minutes 10 seconds in stifling heat, with the temperature climbing to 35C on the 216.5km stage.
The Credit Agricole team, defending Hushovd's yellow jersey, were the first to try to catch the group, some 70km from the finish.
Arrieta then tried his luck alone, but the AG2R rider was gobbled up just before the Cauberg climb, where Kessler broke decisively for victory.
Dutchman Erik Dekker's career ended on a sad note when the Rabobank rider was forced to pull out.
Dekker, 36, crashed along with American Fred Rodriguez after hitting the pavement in the village of Verviers, 59 km from the finish.
Dekker suffered multiple head injuries while Rodriguez suffered wrist and shoulder injuries. Both will undergo precautionary brain scans.
Stage three results:
1 Matthias Kessler (Ger/T-Mobile) 4 hrs 57mins 54secs
2 Michael Rogers (Aus/T-Mobile) +5secs
3 Daniele Bennati (Ita/Lampre)
4 Tom Boonen (Bel/Quick-Step)
5 Erik Zabel (Ger/Milram)
6 Luca Paolini (Ita/Liquigas)
7 Oscar Freire (Spa/Rabobank)
8 Eddy Mazzoleni (Ita/T-Mobile)
9 Georg Totschnig (Aut/Gerolsteiner)
10 Fabian Wegmann (Ger/Gerolsteiner)
43 David Millar (GB - SDV) +5"
131 Bradley Wiggins (GB-Cof) +2:44
1 Tom Boonen (Bel/Quick-Step) 14hrs 52mins 23secs
2 Michael Rogers (Aus/T-Mobile) +1sec
3 George Hincapie (US/Discovery) +5secs
4 Thor Hushovd (Nor/Credit Agricole) +7secs
5 Paolo Savoldelli (Ita/Discovery) +15secs
6 Daniele Bennati (Ita/Lampre)
7 Floyd Landis (US/Phonak) +16secs
8 Vladimir Karpets (Rus/Caisse d'Epargne) +17secs
9 Sergei Gontchar (Ukr/T-Mobile)
10 Matthias Kessler (Ger/T-Mobile)
13 David Millar (Gbr/Saunier Duval) +21secs
152 Bradley Wiggins (Gbr/Cofidis) +9:54