Electrocatalysis is dominated by reaction at the solid–liquid‐gas interface, and the surface properties of electrocatalysts determine the electrochemical behavior. The surface charge (electronic properties) of active sites on catalysts can significantly modulate the adsorption and desorption of intermediates and tune the electrocatalysis. However, there is no direct evidence to bridge the surface charge and catalytic activity of active sites. In this work, we controllably created defects (active sites) on HOPG (highly oriented pyrolytic graphite) surface and broke the intrinsic sp2‐hybridization of graphite by plasma, which induces the localization of surface charge onto defective active sites, as proved by scanning ion conductance microscopy (SICM) and Kelvin probe force microscopy (KPFM). The electrochemical test revealed the significantly enhanced intrinsic activity by the localized surface charge with a volcano relationship. The DFT calculation confirmed the relat
ionship between the surface charge and the catalytic activity. This work correlates surface charge and catalytic activity, which provides the insight into the electrocatalytic behavior and would guide the design of advanced electrocatalysts for various reactions.
