Abstract: Heterogeneous electrocatalysis entails the intricate coupling of electron/proton transfer, adsorption/desorption processes, and mass transport. By enabling in situ monitoring of current–potential responses, voltammetry serves as a highly tunable and exceptionally powerful experimental platform to deconvolute complex interfacial reactions. This review elucidates the fundamental physical significance of the potential and current from both thermodynamic and kinetic perspectives, explicitly correlating them with reaction free energies and rate constants. Accordingly, we systematically analyze how peak shapes, peak positions, and voltammetric trends serve as direct reflections of underlying reaction kinetics and pathways, thereby translating macroscopic observables into mechanistic descriptors. Drawing upon state-of-the-art electrocatalytic case studies, we elucidate the utility of voltammetry in identifying active species and resolving complex catalytic networks. Finally, we provide a comprehensive outlook on the enduring challenges and future evolution of voltammetry.

Key words: Voltammograms, Electrochemistry, Interfacial reactions, Electrocatalysis