Reduction of CO2 has recentiy attracted considerable attention because of its role in climate change and energy cycle. Here, 2-pyridinethiol (Py) is introduced as a new effective electrocatalyst for the reduction of CO2 to methanol on a Pt-Au self-assembled monolayer (SAMs) electrode (Pt-Au-S-Py). 2-Pyridinethiol, which is a solid compound, is one of the thiol derivatives of pyridine and has not been exploited for the reduction of CO2 to methanol. In the present study, using the self-assembled method, 2-pyridinethiol is employed as a heterogeneous electrocatalyst for electrochemical reduction of CO2 to methanol. The reduction of carbon dioxide was carried out at various polarization potentials. Electrolysis of a saturated CO2 solution at Pt-Au-S-Py showed methanol production with a faradic efficiency of 39% at a polarization potential of ? 0.20 V (vs. Ag/AgCl), which is detected by gas chromatography and C-13-NMR spectroscopy. The results revealed that 2-pyridinethiol, as a heterogeneous electrocatalyst, leads to a decrease in the applied reduction potential.