Boullion started karting in 1982 and moved to cars in 1988 after attending a racing school outside Paris. He started racing in the national Formula Ford 1600 series in 1989, finishing third overall, then won the French title in 1990 in dominant fashion. He moved to French Formula 3, placing sixth in 1991 and fourth, with three victories, in 1992.
In 1993, Boullion entered the International Formula 3000 Championship racing for Apomatox, placing eighth in the standings after finishing the season with a pair of second places. Heading into 1994, he switched to DAMS. After a slow start, Boullion went on a streak of four podiums at the end of the year, including winning the final three races, allowing him to narrowly beat Franck Lagorce and Gil de Ferran to the title.
Boullion signed for Williams as a test driver ahead of the 1995 Formula One season but was loaned to Sauber to replace Karl Wendlinger for a majority of the season, starting with the Monaco Grand Prix. Despite crashing at the Nouvelle Chicane during practice and at Massenet in qualifying, he finished the race eighth, having spun off with two laps to go. He spun out of the next race in Canada, then retired from the French Grand Prix with a gearbox issue. At the German Grand Prix, Boullion profited from several engine-related retirements ahead of him to score his first Formula One points, finishing fifth. He placed sixth in Italy, having overtaken Max Papis on the final lap. His final two races ended in retirement: a collision with Mika Salo at the Nürburgring, and a spin at the Pacific Grand Prix which Boullion attributed to Pedro Lamy weaving ahead of him.
In 1996, Boullion returned to his Williams testing role, having been overlooked for a full-time Sauber seat in favour of Johnny Herbert due to his relative inexperience. He remained the Williams test driver in 1997, then became Tyrrell's test driver for 1998.
In 1997, Boullion raced in the Renault Spider Eurocup, finishing fourth with two wins. Having made his 24 Hours of Le Mans debut in 1994, he joined DAMS in the GT1 class in 1997 and retired from both events. In 1998, he raced for JB Racing in the LMP1 category but retired with a gearbox failure. During 1999, Boullion contested the British Touring Car Championship, driving a Renault Laguna for Williams. He scored a lone podium at Silverstone and finished tenth in the standings.
From 2000 onward, Boullion focused on prototype racing. He raced at Le Mans with Racing Organisation Course in 2000, then joined Pescarolo Sport the following year, taking a first success with a win at Magny-Cours in the FIA Sportscar Championship. He remained for 2002, winning the opening and final race alongside Sébastien Bourdais, but missed out on the title to Racing for Holland after missing the round at Brno. After returning for two races in 2003 to take a victory at Estoril, Boullion did not race in 2004 as a result of the FIA Sportscar Championship's demise.
In 2005, he returned to race in the Le Mans Endurance Series, partnering Emmanuel Collard at Pescarolo. The duo won the title with two victories, beating Zytek Motorsport by just two points. That same year, Boullion and Collard, along with endurance-race teammate Érik Comas, finished second overall at the Le Mans 24 Hours. In 2006, Boullion won all five races in the Le Mans Series together with Collard for a successful title defence, despite not racing at Le Mans that year.
From 2007, Pescarolo competed as a privateer against the factory Peugeot outfit. Though the title battle lasted until the final round owing to Peugeot's non-participation at Silverstone, the factory team won, with Boullion settling for the runner-up spot with four podiums from six events. At Le Mans, Boullion scored his second and final podium at the Sarthe, finishing third behind the Audi and Peugeot works entries. In 2008, with Audi entering two cars into the Le Mans Series championship, Boullion scored one podium at the end of the year and finished sixth in points.
In 2009, joined by Christophe Tinseau, Boullion took two second places at the start of the campaign before winning at the Algarve. A retirement at the Nürburgring handed the title advantage to Aston Martin Racing, who took the championship at the final round, leaving Boullion and his teammate in second.
Boullion moved to Rebellion Racing ahead of 2010, where he and Andrea Belicchi scored a sole podium. The pair remained together for 2011, landing two podiums for second in the standings, just three points behind the title-winning Pescarolo squad. Boullion subsequently returned to Pescarolo for 2012, driving in the opening round of the FIA World Endurance Championship at Sebring. He was later slated to race at Le Mans, but a practice crash which damaged his ribs sidelined him from the race.
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