The global climate change has led to great interest in dry reforming of methane (DRM) to produce syngas from two greenhouse gases, CO₂ and CH₄. In order to investigate the reaction characteristics and mechanism under mid-infrared light irradiation, a 10.6 µm CO₂ laser was introduced as an energy source to perform the complete DRM process on Ni/CeO₂ at mild temperature. This scheme was compared with the traditional thermal mode under similar catalyst layer temperature. The laser-driven mode yielded significantly better performance around the DRM light-off temperature of the catalytic system, due to several-fold higher reactant conversion and product selectivity than in thermocatalytic mode. Based on a series of characterizations, the CO₂ laser not only generated more than twice the number of oxygen vacancies than that in thermal mode at pre-reduction stage, but also enhanced the dissociative adsorption of CO₂ and the circulation of oxygen vacancy-reactive oxygen at methane reforming stage. This study provides insight into the mechanism of CeO₂ materials for DRM under mid-infrared illumination.