Semiconductors mediated by rare earth metals (REMs) have attracted attention with regard to the degradation of pollutants. In order to enhance the visible response of TiO2, La-doped TiO2 (La-TO) photocatalysts with visible-light-driven capacity for NO removal were successfully synthesized in this study via a facile sol-gel method followed by calcination. A series of La-TiO2 samples with differing weight ratios were evaluated for their photocatalytic performances. It was found that 3% La integrated with TiO2 (in mass ratio) could enhance the removal efficiency of NO (up to 32%) under solar light, which is more than twice that seen with pure TiO2. The resulting products were characterized by a series of techniques, such as XRD, FTIR, UV-vis DRS, BET and (photo)electrochemical analysis. The results indicated that La-doped TiO2 can harvest visible light due to the relatively narrow band gap (from 2.98 to 2.75 eV). More importantly, La dopant improved electron-hole separation and suppressed charge carrier recombination, due to the synergistic effect. Furthermore, La-doped TiO2 increased the photo-oxidation efficiency of the transformation from NO to NO3–, owing to inhibition of the production of intermediate NO2 (0.02%). To the best of our knowledge, this study is the first time that La-doped TiO2 has been used to eliminate NO (at the ppb level) in the atmosphere. This study provides a facile and controllable route to fabricate La-TO photocatalyst for NO abatement with high selectivity of NO2 under visible light.