This paper reported the electrochemical reduction of CO2 on fluorine doped tin oxide (FTO) semiconductor, which was performed in CO2-saturated 0.1 M NaHCO3 solution using cyclic voltammetry. It was found that a well-defined reduction peak at -0.39 V (vs.SCE) occurs on the cyclic voltammogram (CV), which is direct evidence for the electrochemical reduction of CO2. This result demonstrates that the bare FTO glass electrode possesses good electrocatalytic ability towards CO2 reduction under lower applied potentials. The result from the reduction peak current as a function of scan rate provided strong evidence for the reaction mechanism, i.e., the reduction of CO2 is performed via adsorption of CO2 on the FTO electrode surface and then CO2 is reduced. The main products obtained under a constant potential electrolysis of -0.55 V are methanol and formate, the mass ratio of formate to methanol is approximately 0.54 to 1 based on the result of H-1 NMR.