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In August 2012, Démare won the first World Tour race of his career by prevailing in the Vattenfall Cyclassics, ahead of local favorite André Greipel and Giacomo Nizzolo. Démare clearly dominated the mass sprint contested in scorching heat at the end of the 245.6 km (152.6 mi) race. That year, he also participated in the Olympic road race, finishing 30th.
2013 season
In 2013, Démare won 3 stages in a row at the Four Days of Dunkirk and the general classification. On the third stage, his team-mate and lead-out rider Geoffrey Soupe produced a final power surge to launch Démare, and the duo finished one-two in the mass sprint, with Ramon Sinkeldam of Argos–Shimano taking third place.
2014 season
Démare won the Four Days of Dunkirk stage race for the second year in succession, winning two stages during the event. He also won the points and young rider classifications. He also put in some strong performances in the cobbled classics, finishing second in Gent–Wevelgem and twelfth in Paris–Roubaix.
2015 season
Démare struggled for form for much of the 2015 season, only scoring one top ten finish in the spring classics with a tenth place in Omloop Het Nieuwsblad. He did however manage to score two stage wins in the Tour of Belgium.
2016 season
In January 2016 Démare announced his race plans for the first half of the new season, starting his campaign on home soil at the Étoile de Bessèges and Tour Méditerranéen, followed by competing in the cobbled classics of Omloop Het Nieuwsblad, Kuurne–Brussels–Kuurne, Milan–San Remo, Gent–Wevelgem, Tour of Flanders and Paris–Roubaix, along with the stage races Paris–Nice and the Three Days of De Panne. He also announced that he would skip the Tour de France and focus on the Giro d'Italia instead. He enjoyed success at the Tour Méditerranéen, where his FDJ squad won the race's opening team time trial and he won the following stage. Démare went on to win the first full stage of Paris–Nice and then took the biggest win of his career at the Milan–San Remo. His victory was questioned by rival riders Matteo Tosatto and Eros Capecchi, who alleged that Démare had been assisted by a tow from a team car on the climb up the Cipressa after he crashed with 30 kilometres (19 miles) to go. However, in the absence of any photographic or video evidence, race officials decided not to take any action. Démare became the first Frenchman to win the Milan-San Remo since Laurent Jalabert in 1995. He was also the first Frenchman to win a Monument race since 1997, when Jalabert and Frédéric Guesdon had won the Giro di Lombardia and Paris–Roubaix respectively.
2017 season
On 4 July, two days after finishing Stage 2 in second position behind Marcel Kittel, Démare clinched his first Tour de France or Grand Tour stage win by winning the Tour de France's fourth stage that ended in a hectic sprint into Vittel; it was the first stage victory by a Frenchman in a bunch sprint since Jimmy Casper won Stage 1 that started and ended in Strasbourg in 2006. In Stage 6, Démare was edged out again into a second-place finish by Marcel Kittel, who launched a perfectly timed late sprint with around 200 metres to go. Démare was ill during the mountainous Stage 8 and fell back very early. Two teammates were with him trying to bring him in within the time limit. He eventually finished in 188th position, 37 minutes and 33 seconds behind the Stage 8 winner. Démare, who was sitting in second position in the points classification at the start of the Stage 9, finished that challenging mountain stage in a group around 40 minutes behind the Stage 9 winner. That put him outside the time limit, and therefore out of the Tour de France, along with six other riders.
2018 season
After finishing second to Dylan Groenewegen at Kuurne–Brussels–Kuurne, Démare took his first victory of the season with an opening-day stage win at Paris–Nice. He took third-place finishes on consecutive March weekends at Milan–San Remo and Gent–Wevelgem, but it was not until June before he took another victory, winning the penultimate stage of the Tour de Suisse. At the Tour de France, he was third on the second and thirteenth stages, before he took his second Tour de France stage win, on stage eighteen into Pau, following a lead-out from teammate Jacopo Guarnieri. With a further third-place finish on the final stage, Démare finished third in the points classification. He was second at the EuroEyes Cyclassics, before he completed a clean sweep at the Tour Poitou-Charentes en Nouvelle-Aquitaine, winning all five stages on his way to the overall victory.
2019 season
Démare's first victory of the 2019 season came during the tenth stage of the Giro d'Italia, which ended on the streets of Modena, prevailing in a bunch sprint ahead of Elia Viviani. He took the lead of the points classification the following day, which he held for seven stages, but ultimately finished second to Pascal Ackermann – a rider he had criticised following his Modena stage victory. He then won two stages and the points classification at the Route d'Occitanie, and also won a stage at the Tour de Wallonie. Démare's final win of the season came at September's Okolo Slovenska, where he won the penultimate stage and the points classification; he finished second overall, one second in arrears of race winner Yves Lampaert.
After a stage win in September's Tour de Luxembourg, Démare returned to the Giro d'Italia in October, as one of the contenders for the points classification jersey. Démare won his first stage of the race on stage four, winning a bunch sprint into Villafranca Tirrena. Démare then won the next two bunch sprints on stages six and seven into Matera and Brindisi respectively, taking and solidifying his lead in the points classification, and as a result, becoming the first rider since Robbie McEwen in 2006 to win three stages in the opening week of the Giro d'Italia. He added a fourth stage victory on stage eleven into Rimini, again in a bunch sprint, and ultimately held the points classification lead until the finish in Milan; he finished 49 points ahead of his closest challenger, Peter Sagan. Démare finished the 2020 season with fourteen victories, two more than any other rider.
2021 season
Démare took his first win of the season in April at the one-day race, La Roue Tourangelle, beating Nacer Bouhanni in a sprint finish. He then won two stages and the points classification in the Volta a la Comunitat Valenciana, and in May, won the last three stages of the Boucles de la Mayenne on his way to winning the general and points classifications at the race. He won the second stage of the Route d'Occitanie, before competing in the Tour de France for the first time since 2018. Démare recorded a single top-ten stage finish (fourth) on stage six, and finished outside of the time limit three stages later, ending his race early. He made his first start at the Vuelta a España, looking to complete the triptych of winning a stage at all three Grand Tours. The closest he came was a second-place finish to Fabio Jakobsen on the fourth stage, and he finished inside the top-100 of a Grand Tour general classification for the first time. He finished the season with a second-place finish at Paris–Bourges, and victory in Paris–Tours, winning out of a four-rider group that had broken clear towards the end of the race. He became the first French rider to win the race for fifteen years.
2022 season
Early in the season, Demare finished in 10th place in both Milan-San Remo and Gent Wevelgem. During the 2022 Giro d'Italia he rode very strongly winning three stages as well as the points classification. His victory on stage 13 of the Giro was the 10th grand tour stage win of his career.