Enhancing catalytic efficiency and selectivity is critical issues for CO₂ conversion. The rod-like Cu/N co-doped TiO₂ samples (Cu/N-TiO₂) were synthesized by the electrospinning-calcination method. The substitutional Cu and interstitial N doping not only enhanced visible-light absorption ability, but also formed the Ti(III) sites. The obviously synergistic effect between the photocatalysis and thermalcatalysis appeared for CO₂ conversion over the 8-Cu/N-TiO₂ catalyst. After 9 h visible-light-illumination at 160 ^ºC, the CO, CH₄ and O₂ yields reached 49.7, 1455.1 and 2910.2 μmol/g_cat, respectively. In the 7^th cycling, the yields of two main CH₄ and O₂ products were slightly down by less than 11.5%, and the selectivity of CH₄ product kept above 98%. Combined with the theoretical surface mode, Cu/N co-doping could promote the adsorption-ability for H₂O and CO₂ molecules and reduce activation-energy for CO₂ conversion. Hence, the co-doping construction showed a great significance of designing efficient photothermal catalysts for the CO₂ conversion application.