Mollema took the race by storm with his surprise attack on the downhill with 47 kilometres left to ride on a mountainous day, leaving behind his previous companions in the breakaway on the descent and then holding off the cadre of strong climbers behind on the final climb of the day to take a comfortable win in Quillan.
Mollema celebrated in style as he crossed the line, winning for the second time at the Tour after a win in 2017 into Le Puy-en-Velay.
“It’s amazing to win a stage again," said Mollema after the finish. "I’m super happy. It was a super hard day, it took 80-90 kilometres for the break to go. The team were amazing we didn’t miss any break, we were always in front with four or five guys.
"It was a nice group, a few strong guys but we were not working together so well. I was feeling good, so I thought ‘let’s go from far!’ I did 45 kilometres alone, it was a hard final, I’m happy I made it."
Mollema's attack forced the break to look at each other to decide who would commit to chasing, but none would risk ruining their own opportunity for the stage win and his gap steadily grew into the bottom of the final climb, and then the Dutchman was able to hold off the chasers on the climb and subsequent descent to take the win.
"I was feeling good, I had the confidence that I could ride alone and keep going for a long time," said Mollema. "On the steep part of the last climb, it was important to go full gas and not lose too much. Once I had more than 50 seconds on the top, I was pretty sure I was going to make it.”
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Guillaume Martin (Cofidis) moved up from ninth to second overall with his ride from the breakaway, but Tadej Pogačar (UAE Team Emirates) maintained a comfortable lead at the head of the race, holding over four minutes on Martin in the yellow jersey standings.
The king of the mountains jersey changed torsos on Stage 14, with Michael Woods (Israel Start-Up Nation) taking the lead in the classification off Nairo Quintana (Arkea-Samsic) after a ding-dong battle with Wout Poels (Bahrain-Victorious) throughout the stage.
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The first 85 kilometres were hotly contested for riders looking for a stage win, with teams feeling that it was likely that the attackers would go all the way to the finish. A flurry of attacks at the start of the race drove what was a fast early tempo, but with everyone trying to make the move, everything was marked in the early stages.
Kristian Sbaragli (Alpecin-Fenix) made a lone move, being allowed to go as he cut a lone figure at the head of the race, with four others; Maxime Chevalier (B&B Hotels), Anthony Turgis (TotalEnergies), Jonas Rickaert (Alpecin-Fenix) and Toms Skuijns (Trek-Segafredo) chasing after him on the flat roads.
As the riders hit some inclines on the way into the first categorised climb of the day, more attacks were launched from the peloton and the gap began to reduce rapidly as the race approached the succession of climbs that formed a difficult second half of the stage.
A messy near-catch with the breakaway and a number of attacks made it a complicated situation for the intermediate sprint after 76 kilometres raced. With green jersey holder Mark Cavendish (Deceuninck-QuickStep) not at the front of the peloton, Michael Matthews (Team BikeExchange) beat Sonny Colbrelli (Bahrain Victorious) at the intermediate sprint, the Australian taking nine points and Colbrelli eight.
The attacks continued to flow from the peloton until the base of the first category two climb, the Col de Montségur - 4.2 kilometres long averaging 8.7%. Mattia Cattaneo (Deceuninck-QuickStep) and Wout Poels (Bahrain Victorious) accelerated away from the peloton on the early slopes. Michael Woods (Israel Start-Up Nation) attacked soon after and managed to get across to the front pair.
Omar Fraile (Astana-Premier Tech), Louis Meintjes (Intermarche-Wanty-Gobert Materiaux), Esteban Chaves (Team BikeExchange), Patrick Konrad (BORA-hansgrohe), Guillaume Martin (Cofidis), Sergio Higuita (EF Education-Nippo) and Bauke Mollema (Trek-Segafredo) launched their own attacks and formed together as the main chase group on the climb.
Cattaneo was dropped as Woods and Poels accelerated to contest the mountain points at the top of the climb, Poels just pipping Woods with a well-timed sprint. Cattaneo was able to recover the duo in the valley, just before the next ascent of the Col de la Croix des Morts.
The gap pushed out to the peloton as UAE Team Emirates seemed content to let things go, with Martin the top rider in the general classification in ninth overall, but over nine and a half minutes behind their race leader Tadej Pogačar.
The chasing group drew within 25 seconds at the base of the climb, but the combined pace-making of Woods and Poels at the lead of the race kept the chasers at bay. Woods took the top points on the climb this time, adding another 5 points and moving into the virtual mountains lead.
Valentin Madouas (Groupama-FDJ) and Elie Gesbert (Arkea-Samsic), joined forces Pierre Rolland and Quentin Pacher (both B&B Hotels) had made an optimistic bid to join the move at the front of the race with the gap sitting at a minute and half to the front of the race when they attacked.
The Martin group joined the front trio with 70 kilometres left to the finish line and set a steady pace, increasing their lead on the peloton, but not the Rolland group, who bridged what remained of their deficit to the front of the race joining the breakaway with 55 kilometres to ride, at the base of the Côte de Galinagues - 2.2 kilometres at 9%. Poels took the win at the mountain sprint this time, tightening the battle at the top of the classification.
There was a plateau and downhill run from there into the run into the final climb of the day, with four minutes lead to play with over the peloton with 50 kilometres left in the race. Woods crashed on the descent, washing out his front wheel and having to chase back onto the attackers.
Mollema attacked on the downhill, moving clear with 43 kilometres to go and pushing out his lead steadily, with his former breakaway companions uncooperative in the chase behind. Mollema hit the final climb of the day, the Col de Saint-Louis with a minute and a half lead, the 4.7-kilometre climb at an average of 7.4% the last chance for the climbers in the chasing group to catch Mollema.
After a series of attacks, Cattaneo, Woods, Konrad and Higuita emerged as the top climbers in the chase, forming a quartet that crested the top of the climb a minute behind Mollema and set off on the chase to attempt to catch the Dutchman.
The rest of the breakaway was a further 30 seconds behind by the summit, with Mollema the heavy favourite to win with just the descent to Quillan to come. The Dutchman soloed in for a convincing win, arms wide in celebration as he crossed the line.
Konrad just beat out Higuita in the sprint for second, with the Colombian third.
In the peloton, it was a relatively quiet day without any attacks, but it was still a heavily reduced main bunch that rolled into the finish, with Pogačar retaining the race lead and Martin jumping up into second overall with his performance.
The Tour de France continues in the Pyrenees with the queen stage of the 2021 edition, with the highest point of the race coming atop the Port d’Envalira in the latter half of the stage. Watch from 2030 AEST on SBS and SBS OnDemand, with the SKODA Tour Tracker starting slightly earlier at 2010 AEST.