Metallic nickel nanostructures that were partially decorated by discrete nickel oxide layers were fabricated by in situ reduction of calcinated Ni‐containing layered double hydroxide nanosheets, the structure of which was confirmed by extended X‐ray absorption fine structure spectroscopy, X‐ray photoelectron spectroscopy, and transmission electron microscopy. The existence of the abundant interfaces between the surface Ni oxide overlayer and metallic Ni altered the geometric/electronic structure of the Ni nanoparticles, making them apt for CO activation under light irradiation. Most importantly, the unique structure favors the C−C coupling reaction on its surface, which confers the catalyst unexpected reaction power towards higher hydrocarbons at moderate reaction conditions. This study leads to a green and sustainable approach for the photocatalytic production of highly valuable chemical fuels. Production of hydrocarbons: Oxide‐decorated metal nickel nanoparticle catalysts were prepared and used for the photocatalytic hydrogenation of carbon monoxide to C2+ hydrocarbons in visible light. The work highlights the possibility of using solar energy to produce fuels and chemicals under mild reaction conditions.