Garmin-Sharp’s Martin won his first stage on the Tour, out-sprinting Denmark’s Jakob Fuglsang (Astana) in a two-man shootout at the end of the 165.5km stage from Saint-Girons to Bagneres-de-Bigorre.
But the story of the day was race leader Froome having to ride the best part of 130km in isolation after all his Sky team-mates – including the Australian Richie Porte – were blown off the back of the main pack in a brutal opening hour of racing.
Porte – so impressive on Saturday after finishing second to Froome in Ax 3 Domaines – teetered on the opening climb of the day before bring dropped definitively on the second ascent, the Col de Mente, to finish the stage 18 minutes in arrears and plummet from second to 33rd on the general classification.
A series of attacks from Garmin ahead of the first of five climbs opened the race from the outset, with Jack Bauer, David Millar, Tom Danielson, Ryder Hesjedal, Andrew Talansky and eventual stage winner Martin all heavily involved.
The Saxo-Tinkoff and Movistar teams of Alberto Contador and Alejandro Valverde also rode an aggressive stage, piling the pressure on Froome from kilometre zero – pressure which intensified after the unexpected cracking of Froome’s main lieutenant, Porte.
Losing young British climber Peter Kennaugh hardly helped, the 24-year-old crashing on the side of the road and disappearing into dense undergrowth in a ditch.
"Yesterday was one of our best days whereas today was one of the toughest," said Sky manager David Brailsford. "Those who said the race was over may think again. I give credit to Garmin and Movistar for taking the race on and making it exciting."
Froome finished safely in the main pack of riders, which was led over the line by the young Pole Michael Kwiatkowski, 20 seconds behind leading duo Martin and Fuglsang.
After Porte’s bad day in the office, Spaniard Valverde rose to second on the overall standings, one minute and 25 seconds down on Froome. Dutch pair Bauke Mollema and Laurens Ten Dam, of Team Belkin, are third and fourth on GC, at 1:44 and 1:50 respectively.
Froome’s main rival, Spain’s Contador, is sixth at 1:51 while stage winner Martin rises into the top 10 to eighth place, 2:28 in arrears.
Irish climber Martin was ecstatic about his victory – and told Eurosport before rising onto the podium that it was part of a carefully executed plan.
"Last year was a procession behind Team Sky so we wanted to show what we could do and put them under pressure," the 26-year-old said.
"It was an incredible effort today from the whole team. We really made the race and from the start we were in breakaways."
Having made numerous attacks early in the stage, Martin made his decisive move the main on the final climb of the day, the Cat.1 La Hourquette d’Anzican, 34km from the finish, taking Denmark’s Fuglsang with him.
The pair crossed the summit with 33 seconds over the main pack and maintained this lead on the long downhill stretch to the finish in Bigorre.
"I don’t think one guy would have survived alone today so I was happy when Jakob came with me. He’s a super-strong rider," said Martin, winner of this year’s Liege-Bastogne-Liege spring classic.
"I knew the last 30km, I knew the last corner was crucial and I knew that I was a better sprinter than Jakob. After the year I’ve had there was the belief and the calmness, which helped too."
Despite being isolated for much of the day, Froome withstood numerous attacks and inter-team alliances to retain his yellow jersey going into the much-needed opening rest day of the race.
After Garmin’s initial animation, it was the constant pressure of the Movistar team which had Froome seemingly on the ropes.
Movistar dominated proceedings for much of the afternoon, with six riders driving the pace over most of the climbs – including Valverde, the Colombian white jersey Nairo Quintana, Spanish national time trial champion Jonathan Castroviejo and Tour de Suisse winner Rui Costa of Portugal.
A long flat drag between the Col de Mente and the Col de Peyresourde saw Valverde and team-mate Ruben Plaza ride clear of the main pack in pursuit of a large leading group of 15 riders, prompting a response by Froome.
The race calmed down ahead of the Peyresourde, with a large pack forming around the yellow jersey while one group of five riders rode two minutes up the road. Porte, meanwhile, rode alongside four Sky team-mates in a chasing group a further two minutes off the pace.
Like his compatriot Porte, former Tour winner Cadel Evans was also distanced on the first climb – but the BNC veteran was able to fight back, and despite needing to change bikes at the foot of the Col de Mente, Evans had ridden back to the yellow jersey group.
Alongside Canada's Hesjedal, Frenchman Pierre Rolland (Europcar) was one of the leading five riders on the Peyresourde, and the 26-year-old picked up enough points to move above Froome in the KOM standings before fading on the final climb.
The last escapee to be reeled in was the impressive Tour debutant Romain Bardet of Ag2R-La Mondiale, who was caught by the Movistar-led pack moments before Quintana made a series of three attacks in a bid to distance Froome.
Each attack failed – and in between the second and third attempts, Martin and Fuglsang had made their decisive move.
Despite seeing his friend and right-hand man Porte drop down the standings, Froome was upbeat at the finish after a what proved to be a baptism of fire for his first ever day in yellow.
"I did feel in control and, tactically, I was able to sit on the wheel of the Movistar riders," he said.
"Given their amazing work yesterday, it’s quite normal for my team-mates to be feeling it today. They are human and that’s bike racing," he added.
Brailsford was also unconcerned about the events of the say, claiming: "Physically, Froome wasn’t worried all day, which is a good thing."
After a rest day on Monday, the Tour resumes on Tuesday with the flat 197km stage 10 which should give the sprinters a chance to return to the fold after two brutal days in the high mountains.