The electrochemical process has emerged as a sustainable energy production technology, utilizing only electricity and water without carbon emissions. In this talk, we will discuss the discovery of a high step site density graphene-derived electrocatalyst, showing promising potential for C2 production in CO2 electroreduction reaction. As a follow-up project, we aim to explore how insufficiently grown graphene can be utilized as an oxidation-controlling mask for selective oxide layer decoration onto a high-step site density electrocatalyst, a challenging task using current existing methods. By incorporating high step site density and Cu/Cu2O interfaces, we successfully improved CO binding stability and enhanced the favorable characteristics for C–C coupling. These findings were supported by electrochemical analyses, underscoring the importance of precise surface structure control in modulating reaction pathways.