Born on 27 December 1985 in Etterbeek, Brussels, d'Ambrosio entered competitive motorsport through karting in 1999 and was a Belgian triple champion by 2002. He then spent four seasons in various Formula Renault categories, won the inaugural International Formula Master title in 2007, and earned his GP2 opportunity with the prominent French outfit DAMS for the 2008 season.
D'Ambrosio made his GP2 Series debut in 2008 alongside entries in the newly created GP2 Asia Series, competing in both championships under the DAMS banner. He finished eleventh in each, collecting two podiums in the main series and two in the Asia Series. The results were modest but established his footing in the category and cemented his relationship with DAMS heading into the following year.
In the 2008–09 GP2 Asia Series, d'Ambrosio stepped up markedly, finishing as vice-champion behind Kamui Kobayashi with four podium finishes. The main-series season that followed was more uneven; he collected three podiums in the opening four rounds but faded through the remainder of the calendar, ending ninth in the final standings. The Asia Series result in particular underlined his capacity to challenge consistently when conditions allowed.
The 2010 GP2 Series season was d'Ambrosio's most significant in the category. Racing again for DAMS, he secured his maiden championship victory at Monaco — one of the most prestigious individual rounds on the calendar — demonstrating the precision and patience that street-circuit racing demands. He subsequently claimed his first GP2 pole position at his home event at the Circuit de Spa-Francorchamps, though a retirement while leading denied him the result. A further podium at Monza rounded out his campaign, and he ended the season twelfth in the standings — a placing that did not reflect the quality of individual performances he had produced.
D'Ambrosio's GP2 career with DAMS attracted sufficient attention from teams at the top of the sport. In January 2010, he was named Reserve Driver of the Renault F1 team, and he made four practice appearances with Virgin Racing at the 2010 Singapore, Japanese, Korean, and Brazilian Grands Prix. On 21 December 2010, Virgin confirmed him as a race driver for the 2011 Formula One World Championship, replacing Lucas di Grassi.
D'Ambrosio's GP2 record is that of a technically refined, consistent performer who peaked at the right moment. His breakthrough victory at Monaco came on a circuit that punishes errors relentlessly, and his vice-championship in the Asia Series showed he could sustain pressure over a short campaign. The three seasons under DAMS gave him the mechanical sympathy and race-management skills he later brought to a seven-season Formula E career, in which he won three races and led a championship table mid-season. He went on to senior team management roles, culminating in his appointment as Deputy Team Principal of Scuderia Ferrari and Head of the Ferrari Driver Academy in 2024.