With the yellow jersey in his sights, Martin (Etixx-QuickStep) launched an inspired attack out of the remnants of the peloton with three kilometres to go to finish a single second ahead of John Degenkolb (Giant-Alpecin) and Peter Sagan (Tinkoff-Saxo).
Martin began the stage just two seconds behind Chris Froome (Sky), having missed out on the yellow jersey by a matter of seconds on each of the first three stages. Today's attack, which brought him home ahead of the pack plus 10 bonus seconds from the win means he leads the race by 12 seconds.
Froome now sits in second place while BMC’s Tejay van Garderen is third at 25 seconds at the end of the 228.5km stage from Seraing to Cambrai.
Martin took the win despite puncturing in the final major cobbled section.
"I had a flat tyre in the last cobbled section. I had to change to Matteo [Trentin']s bike," said Martin.
I wasn't really thinking about anyone following me when I attacked," he added. "Maybe they thought I was more on the limit than what I actually was when I launched in that moment. It's also possible no one expected such an early attack. I think inside four kilometres to go everyone was on their hands and knees. It was just the right moment for me to try my chance."
Seven cobbled sections were on the menu and the expectation was that the Tour would again see another day of dramatic racing designed to test of the peloton.
However the largely dry conditions reduced the complexity of the stage in favour of all the major general classification contenders who safely navigated the potentially treacherous terrain while producing an engrossing racing spectacle.
Lieuwe Westra (Astana), Thomas De Gendt (Lotto-Soudal), Perrig Quémeneur (Europcar) and Frédéric Brun (Bretagne-Séché Environnement) broke away to a lead of 9min 10sec but lost it all after the peloton encountered the second cobbled secteur with 40km to go.
From that point it was a battle for position among the 'big four' of Froome, Alberto Contador (Tinkoff-Saxo), Nairo Quintana (Movistar), defending champion Vincenzo Nibali (Astana) and those who believed they could win the stage.
Nibali was the most aggressive with repeated thrusts on the longer sections of pave, but he could not shake off his rivals at any point. A late attack spearheaded by Froome and team-mate Geraint Thomas created a small split in the last 10km, but was brought back by Tinkoff-Saxo a few kilometres before Martin attacked.
"I knew if I could make it to the last kilometre, which was a little more technical with the cobbles and the hard left-hand turn, I would have a chance," said Martin. "The last three days I missed the yellow by just a few seconds. My goal was to get it on the first day and I was sad I missed it. Today I was really motivated."
The biggest loser on the stage was outside podium chance Thibault Pinot (FDJ.fr) who suffered an untimely flat at a crucial stage and was unable to rejoin a disappearing peloton. The Frenchman finished third in 2014 but the day's result left him with no chance of a repeat.
”I had a mechanical and then it went full gas," Pinot said. "When incidents pile up… It was the same in 2013 and it looks like it's going to be the same again. It's a shame.
”Now I will try to recover with time. I'm going to finish the Tour and try to prove that my talent is still there."
Froome remains the best-positioned of the general classification favourites, leading his nearest major rival Tejay Van Garderen by 13 second and Alberto Contador by 36 seconds.
"I’m not concerned about losing the yellow jersey," said Froome. "There’s a long way to go, and while Tony’s a great time triallist, he’s not going to be there in the mountains, so I’m happy to see the jersey go to him rather than any of the big overall rivals.
Martin hopes to retain the maillot jaune until the first rest day next week.
"There are a few hard finishes, but I believe I can stay in front with the support of my team. We also have the team time trial coming up," he said. "I think we have a fighting chance of holding on to this jersey until the first rest day."