Born in Chartres, France, Duval began his career in karting before progressing to single-seater formulae. He won the Formula Campus France title in 2002 and the Formula Renault 2000 France championship in 2003. In 2004, he competed in the Formula 3 Euro Series, finishing eleventh with two podiums, and tested for the Renault F1 team. The following year he finished sixth in the F3 Euro Series and scored a pole position at the Macau Grand Prix. He then relocated to Japan to compete in Formula Nippon and Super GT.
Duval spent several years building his reputation in Japan, competing in Formula Nippon from the mid-2000s. After finishing second in the 2008 championship, he won the 2009 Formula Nippon Championship with four victories, driving for Nakajima Racing. That title established him as a front-rank driver in Japanese motorsport.
His endurance racing career with Audi Sport proved equally distinguished. He won the GT2 class at the 24 Hours of Le Mans in 2005 driving a Porsche, and later became an Audi factory driver. Competing in the Le Mans Series in 2008 alongside Alexandre Prémat, he won the LMP1 title at the 1000 km of Silverstone after a race incident removed the leading Peugeot. The crowning achievement of this phase came at the 2013 24 Hours of Le Mans, where Duval co-drove the Audi R18 with Allan McNish and Tom Kristensen to overall victory, one of the most experienced co-driver pairings in the race's modern era.
His endurance career was briefly disrupted at Le Mans in 2014, when his Audi was severely damaged in an accident during qualifying, though Duval escaped with a small flesh wound.
Duval competed in the Deutsche Tourenwagen Masters as part of his Audi factory programme. His DTM career ran alongside his endurance commitments, representing Audi's presence across multiple categories during the early-to-mid 2010s. His performances in the series contributed to Audi Sport's competitive programme while he continued his Le Mans and FIA WEC efforts in parallel.
Duval made his Formula E debut at the 2015 Miami ePrix, joining Dragon Racing mid-season and replacing Oriol Servià to partner Jérôme d'Ambrosio. Despite missing the opening four rounds of the inaugural 2014–15 season, he made an immediate impact, scoring his first podium with a third-place finish at the Berlin ePrix while his teammate d'Ambrosio won, giving Dragon Racing their first double podium. Duval added a further podium at the London ePrix season finale, ending the campaign ninth in the standings with 42 points across seven rounds. His contributions helped Dragon Racing finish second in the teams' championship after starting the year outside the top five.
In the 2015–16 season, Duval started strongly by outqualifying teammate d'Ambrosio in the opening two rounds. He registered a fourth-place finish in Beijing and nearly reached the podium in Putrajaya before crashing while fighting for position in the closing stages. At Punta del Este, he and d'Ambrosio locked out the front row, Dragon Racing's first such achievement, with Duval finishing fourth just two tenths behind his teammate.
Duval continued to balance Formula E with endurance commitments before eventually returning full-time to sportscar racing. He joined Peugeot Sport for the FIA World Endurance Championship's Hypercar era, racing the Peugeot 9X8 in the top class.
Duval accumulated 42 victories across the various categories he raced in, a figure that reflects the breadth of a career spanning formula cars, touring cars, endurance prototypes, and electric single-seaters. His Le Mans overall win in 2013 alongside two legends of the event remains the centrepiece of his career. As an Audi factory driver through the manufacturer's dominant era at Le Mans, he was part of one of the most successful factory programmes in endurance racing history.