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 °C, the CO, CH4 and O2 yields reached 49.7, 1455.1 and 2910.2 µmol/gcat, respectively. In the 7th 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.