The rational design and in deep understanding of efficient, affordable and stable materials to promote the light-assisted production of fuels and commodity chemicals is very appealing for energy crisis and climate change amelioration. Herein, we have prepared a series of Co-doped hydroxyapatite (HAP) catalysts with different Co content. The materials structure has been widely investigated by XRD, FT-IR, HRTEM, XPS, XAS, as well as computational simulations based on Density Functional Theory (DFT) with PBE functional. At low Co loading, there is a partial substitution of Ca cations in the HAP structure, while higher loadings promote the precipitation of small (∼ 2 nm) Co nanoparticles on the HAP surface. For the optimal Co content, a constant CO rate of 62 mmol·g−1·h−1 at 1 sun illumination and 400 °C, with the material being stable for 90 h. Visible and NIR photons have been determined responsible of the light-assisted activity enhanced. Mechanistic studies based on both experimental and DFT simulations show that H2 preferentially adsorbs to metallic Co, while CO2 adsorbs to the HAP surface oxygen. Moreover, both direct photo- and plasmon-driven contributions have been separated in order to study their mechanisms independently.