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.