Duval began his career at the international level in 1999, winning the Belgian Citroën Saxo Challenge title with four victories. He competed in the inaugural season of the Super 1600 category of the World Rally Championship and later in the Junior World Rally Championship aboard a Ford Puma in 2001.
Beginning with the 2002 season, he became a regular driver of a Ford Focus RS WRC with the factory M-Sport-ran Ford World Rally Team. In the same year, he took a category win on the Monte Carlo Rally in the junior series.
For the 2003 season, Duval was promoted to the role of regular Ford points-scorer in the manufacturers' championship, alongside Markko Märtin, after the departure of Colin McRae and Carlos Sainz. He made a points-scoring debut on that year's Monte Carlo Rally and collected his first world rally podium in Turkey later in the year. He retained his role alongside Märtin for the 2004 season, backing up the Estonian in a 1–2 early season win on the Rally Mexico. Both Duval and Märtin were released from their contracts at the end of the 2004 season amidst uncertainty about Ford's future participation.
Duval moved to reigning world champion manufacturers Citroën for the 2005 season, partnering Sébastien Loeb and driving the Xsara WRC. His Citroën debut in Monte Carlo ended with a crash from second place, leading to a two-rally leave for the Turkey and Acropolis rallies. He was replaced by Carlos Sainz, described in the corpus as Duval's idol, a double world champion, and the immediate Citroën predecessor. By late 2005, Duval recovered his form, finishing second on the Rally Deutschland, behind Loeb. He added a second-place finish on the Wales Rally GB, an event that was "somewhat ill-starred by the fatal accident that befell erstwhile Ford teammate Markko Martin's navigator, Michael Park." Later that year, at the 2005 Telstra Rally Australia, Duval won his first World Rally Championship event, ahead of Harri Rovanperä and Manfred Stohl, following the exits of several podium challengers.
Citroën took a one-year sabbatical from the series, and Duval was unable to maintain a link with either Citroën or the privateer Kronos outfit in 2006. He competed sporadically in a privately run Škoda Fabia WRC, with a best finish of sixth on the Rally Catalunya in Spain. He achieved only two other top ten finishes that year, on the Italian and Turkish rounds, but won his native non-world championship Condroz Rally in November.
Despite funding issues forcing him to abort a proposed campaign for the 2007 season, Duval secured a deal to drive a Kronos run Citroën Xsara WRC later in the year. He finished second to Loeb on the 2007 Rallye Deutschland, marking his first podium since his sole World Rally victory.
In the 2008 season opener, the Monte Carlo Rally, Duval competed in a Ford Focus RS WRC 07 for Stobart VK M-Sport Ford, finishing fourth after a tight battle for third place with Chris Atkinson, separated by only 1.1 seconds. He returned to Stobart Ford for the 2008 Rallye Deutschland and beat Mikko Hirvonen for third place. After Gigi Galli was injured, Duval was signed by Ford as his replacement for gravel events, and promoted to the factory team for tarmac events. He finished fourth at the Rally Catalunya and third at the Tour de Corse.
During the 2008 season, on the Japanese circuit, Duval went off the road on stage 6 and crashed into a concrete barrier, seriously injuring his co-pilot, Patrick Pivato, who suffered a fractured pelvis and a fractured leg.
Duval announced his retirement from rallying in March 2010 but changed his mind to compete in the Rally Deutschland the same year in a Stobart Ford. He crashed during SS14 Arena Panzerplatte 2 and retired from fifth position.
In 2015, Duval was sentenced to four months in prison for his involvement in a car insurance fraud scheme.
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