Highly efficient CO2 reduction to produce fuel driven by solar energy is of great significance to alleviate the greenhouse effect and realize solar energy storage. Herein, a unique nanocomposite of MgO‐cluster‐modified Ni nanoparticles supported on Ni‐doped MgO (MCM–Ni/Ni–MgO) is synthetized by a simple approach. Very high fuel production rate for H2 and CO (78.01 and 88.44 mmol min−1 g−1) as well as a large light‐to‐fuel efficiency (31.7%) are achieved by photothermocatalytic CO2 reduction by CH4 on MCM–Ni/Ni–MgO merely using focused UV–vis–IR illumination. This arises from efficient light‐driven thermocatalysis that is further enhanced by a photoactivation due to the activation energy being considerably reduced upon the illumination. More importantly, it exhibits excellent photothermocatalytic durability due to its extremely low carbon deposition rate of 8.85 × 10−4 gc h−1 g−1 catalyst, reduced by 39.2 times as compared with that of a reference sample of Ni nanoparticles supported on Ni‐doped MgO (Ni/Ni–MgO). The experimental evidences and the functional theory calculations reveal that the surface modification of Ni nanoparticles by MgO cluster not only inhibits the carbon deposition side reactions of CO disproportionation and CH4 complete dissociation, but also significantly accelerates the oxidation of carbon species, thus tremendously decreasing carbon deposition rate.