Citroën signed Neuville for the 2012 World Rally Championship, driving selected races in a Citroën DS3 WRC for their junior team. The season saw Neuville make his World Rally Car-debut. At the season opener in Monte Carlo, Neuville crashed out of the event early. He remained scoreless until the fourth round in Portugal where he finished in eight position. Prior to Portugal, he had won his first stage win in Mexico. In Argentina, he was fifth, despite rolling his car early in the event. Neuville's results had so far been plagued by the use of Rally 2-rules, his first error-free event was in Acropolis where he was sixth. Neuville's season did not include New Zealand with the Citroën Junior Team, but as Nasser Al-Attiyah in the Qatar World Rally Team was injured and unable to compete, Neuville replaced him for the Qatari team in the event. He was battling for fifth place with fellow World Rally Car-rookie Ott Tänak, with Neuville eventually securing the position due to Tänak retiring. He scored no points in Finland after crashing from sixth place. He was running close of a podium finish in the following event in Germany, but, like in Finland, he was outside the points due to a crash. He returned to the points by finishing seventh in Wales. His best result of the season came in France, where he led a World Rally-event for the first time in his career and eventually finished fourth, after many stage wins. Another outing for the Qatar team in Sardinia, the penultimate event of the season, meant Neuville contested the full season. He was outside the points in Sardinia, as well as in Catalunya, the final event of the season, due to incidents on both rallies. He finished the season in seventh position.