The reformation of CO 2 through photocatalytic processes to obtain products with high energy value and compatibility with the current energy infrastructure is a compelling strategy to minimize the emission of CO 2 into the atmosphere, one of the main greenhouse gases. However, practical application of such a photocatalytic system requires significant efforts for improved CO 2 photoreduction performance and product selectivity. Thus, in the present work, CuO nanoparticles were combined with Nb 2 O 5 in order to improve the photocatalytic properties of these semiconductors in the CO 2 photoreduction process. Nb 2 O 5 / CuO heterojunctions were prepared via a solvothermal treatment method, while the experimental tools, such as FESEM, HRTEM, and DRS, were employed to evaluate the microstructural and electronic properties. We describe how CuO decoration over Nb 2 O 5 adjusts its selectivity for CO 2 reduction to CH 4 , HCOOH, or H 3 CCOOH in different contents. An investigation of CO 2 photoreduction using different electron donors/scavengers (water, sodium oxalate, and potassium bromate) under ultraviolet radiation revealed that its decoration influences local CO production by modifying the selectivity. CO has been confirmed as the main intermediate for HCOOH and CH 3 COOH production, and CO 2 reduction efficiency increases at low CuO content (2.5% wt), leading to the formation of soluble hydrocarbons, and increases for CH 4 in higher amounts (10% wt).