Electrochemical reduction of CO2 has the benefit of turning greenhouse gas emissions into useful resources. We performed a comparative study of the electrochemical reduction of CO2 on stepped Pb(211) and Sn(112) surfaces based on the results of density functional theory slab calculations. We mapped out the potential energy profiles for electrochemical reduction of CO2 to formate and other possible products on both surfaces. Our results show that the first step is the formation of the adsorbed formate(HCOO*) species through an Eley-Rideal mechanism. The formate species can be reduced to HCOO- through a oneelectron reduction in basic solution, which produces formic acid as the predominant product. The respective potentials of forming HCOO* are predicted to be -0.72 and -0.58 V on Pb and Sn. Higher overpotentials make other reaction pathways accessible, leading to different products. On Sn(112), CO and CH4 can be generated at -0.65 V following formate formation. In contrast, the limiting potential to access alternative reaction channels on Pb(211) is -1.33 V, significantly higher than that of Sn. Electrochemical reduction of CO2 has the benefit of turning greenhouse gas emissions into useful resources. We performed a comparative study of the electrochemical reduction of CO2 on stepped Pb (211) and Sn (112) surfaces based on the results of density functional theory slab calculations. We reported the potential energy profiles for electrochemical reduction of CO2 to formate and other possible products on both surfaces. Our results show that the first step is the formation of the adsorbed formate (HCOO *) species through an Eley-Rideal mechanism. The formate The can potentiate of HCOO * are predicted to be -0.72 and -0.58 V on Pb and Sn. Higher overpotentials make other Reaction pathways accessible, leading to different products. On Sn (112), CO and CH4 can be generated at -0.65 V following formate formation. potential to access alternative reaction channels on Pb (211) is -1.33 V, significantly higher than that of Sn.