The hydrogenation of CO2 into hydrocarbons promoted by the action of sunlight has been studied on Co nanoparticles covered by thin carbon layers. In particular, nearly 100% selectivity to hydrocarbons is obtained with increased selectivities towards C2 + hydrocarbons and alcohols (mainly ethanol) when using nanostructured materials comprising metallic cobalt nanoparticles, carbon layers, and sodium as promoter (NaCo@C). In the contrary, larger amount of CH4 and lower selectivity to C2 + hydrocarbons and alcohols were obtained in the conventional thermal catalytic process. When using Co@C nanoparticles in the absence of Na or bare Co3O4 as catalyst, methane is essentially the main product (selectivity > 96%). Control experiments in the presence of methanol as a hole scavenger suggest the role of light in generating charges by photon absorption as promoting factor. The reaction mechanism for photoassisted CO2 hydrogenation on the Co-based catalysts was investigated by near ambient-pressure X-ray photoelectron (AP-XPS) and in situ Raman spectroscopies, which provided information on the role of light and Na promoter in the modulation of product distribution for CO2 hydrogenation. Spectroscopic studies suggested that surface CO2 dissociation to CO, the stabilization of CO adsorbed on the surface of Na-Co@C catalyst and the easy desorption of reaction products is a key step for photothermal CO2 hydrogenation to ethanol and C2 + hydrocarbons.