Electrochemical conversion of CO2 to fuels or stock chemicals with high-energy density would be a major step forward in the introduction of a carbon neutral energy cycle. One of the achievements in electrochemical CO2 reduction is the clarification of the catalysts toward two-electron involved products such as CO and formate. Interestingly, CO/formate ratio can be selectively controlled on formate selective catalyst such as Sn by tuning the interfacial electric field. On the other hand, on copper catalyst, the selection of alkali cations has direct influence on activity and product selectivity; increasing the size of mono-valent cations can increase the activity and selectivity toward C-C coupled products by modulating the interaction energy between adsorbates and electric fields at the interface. In addition, copper catalyst with a specific atomic-scale gap accelerates the reaction kinetics and selectivity to C2+ products. Therefore, understanding the roles of catalyst, support and electrolyte offers the design of efficient, yet cheap electrochemical CO2 reduction systems.