Jan Bakelants of Belgium held off the chasing pack to win an eventful second stage of the 100th Tour de France and take the race leader's yellow jersey.
Peter Sagan was second and Michal Kwiatkowski third in the 156km stage.
Britain's David Millar moved to second overall, while first-day leader Marcel Kittel of Germany dropped back.
Pre-race favourite Chris Froome came home in the peloton after riding clear of the bunch on the final climb of the day, 12km from the finish in Ajaccio.
The British Team Sky rider followed team-mate Richie Porte up the first 700m or so of the one-kilometre climb before leaving his rivals with a sharp burst of speed as he chased down Cyril Gautier who had gone clear on the ascent.
"I knew the descent was tricky and dangerous," Froome said. "I was on the front with Richie and I thought it might be a good time, just to push on a little bit, get ahead and take the descent at my own pace and stay out of trouble.
"It's always good to keep people on their toes."
Spain's Alberto Contador, who has won the race twice and is likely to be Froome's main rival, also finished in the peloton but was feeling the effects of crashing on Saturday.
He tweeted: "Already relaxed at my room, today uncomfortable on the bike after the crash of yesterday but I passed the day without problems."
Staying out of trouble was key for many riders after Saturday's crash-strewn and controversial opening stage which saw a team bus wedged on the finish line.
Stage two's scare came inside the final 5km as a dog wandered across the road in front of the peloton.
The incident came as six riders were establishing a lead and the platform that would eventually see 27-year-old Bakelants, who is riding in his first Tour de France, win the first stage of his professional career.
The RadioShack Leopard rider went for glory with more than one kilometre remaining and held on for the victory as Sagan, who had been tipped by many to win the stage, led the peloton home one second behind.
"I knew I couldn't win in a sprint so I gambled and gave everything I had," said Bakelants. "I thought of my room mate Jens Voigt and just pedalled. I had to wait five years but what a victory.
"In the end I was thinking, 'Come on! Are we going to ride and be the first six riders or are we just going to wait for the bunch to come back and see another win of Sagan?'
"I think it's going to be a short night tonight; I don't think I'll sleep much."
The race began in Bastia on the north coast of Corsica and weaved its way across the Mediterranean island to the capital Ajaccio in the south west.
Lars Boom, who was involved in a breakaway on stage one, again went clear, with three other riders, early on stage two and won the intermediate sprint.
Andre Greipel led Sagan and Mark Cavendish over the line as the green points jersey contenders in the peloton battled for precious points.
However, the hilly terrain that followed quickly accounted for several of the sprint specialists such as Cavendish and Kittel, who, as race leader, was wearing the yellow jersey - the duo eventually finished in a group more than 17 minutes behind the winner.
Sagan managed to make it over the day's highest climb, which peaked at 1,163m above sea level, with the main bunch to keep alive his hopes of a stage win.
However, attacks on the short-sharp final climb of the day, just 12km from the finish, stretched his Cannondale team-mates and when Sylvain Chavanel went clear with seven kilometres remaining, Sagan's team was unable to respond.
Bakelants could though and he and four other riders worked hard for 5km before the Belgian made his successful solo bid.
Stage two result:
1. Jan Bakelants (Bel) RadioShack - Leopard 3 hours, 43 minutes, 11 seconds.
2. Peter Sagan (Slo) Cannondale +1"
3. Michal Kwiatkowski (Pol) Omega Pharma-QuickStep
4. Davide Cimolai (Ita) Lampre - Merida
5. Edvald Boasson Hagen (Nor) Team Sky
13. David Millar (GB) Garmin-Sharp same time
35. Chris Froome (GB) Team Sky
83. Peter Kennaugh (GB) Team Sky
182. Mark Cavendish (GB) Omega Pharma-Quickstep +17'35"
195. Ian Stannard (GB) Team Sky
196 Geraint Thomas (GB) Team Sky
Overall standings after stage two:
1. Jan Bakelants (Bel) RadioShack - Leopard 8 hours, 40 minutes, 03 seconds
2. David Millar (GB) Garmin-Sharp +1"
3. Julien Simon (Fra) Sojasun
4. Daryl Impey (SA) Orica GreenEdge
5. Edvald Boasson Hagen (Nor) Team Sky
10. Cadel Evans (Aus) BMC Racing same time
11. Nicolas Roche (Ire) Saxo-Tinkoff
18. Chris Froome (GB) Team Sky
51. Peter Kennaugh (GB) Team Sky
81. Alberto Contador (Spa) Saxo-Tinkoff
160. Mark Cavendish (GB) Omega Pharma-Quickstep +17'35"
191. Ian Stannard (GB) Team Sky
198. Geraint Thomas (GB) Team Sky
Green points jersey standings:
1. Marcel Kittel (Ger) Argos-Shimano 47 points
2. Peter Sagan (Slo) Cannondale 43
3. Alexander Kristoff (Nor) Katusha 41
4. Lars Boom (Ned) Belkin 40
5. Danny Van Poppel (Ned) Vacansoleil 39
12. Andre Greipel (Ger) Lotto Belisol 21
20. Mark Cavendish (GB) Omega Pharma-QuickStep 17