Raman probing of carbon electrode and electrolyte under dynamic conditions is performed here using different aqueous electrolytes to elucidate the fundamental events occurring in electrochemical superca-pacitor during charge-discharge processes.The areal capacitance ranges from 1.54 to 2.31 mF cm-2 and it is determined using different techniques.These findings indicate that the Helmholtz capacitance governs the overall charge-storage process instead of the space charge(quantum)capacitance commonly verified for HOPG electrodes in the range of～3 to 7 μF cm-2.Molecular dynamics simulations are employed to elucidate the origin of the reversible Raman spectral changes during the charge-discharge processes.A correlation is verified between the reversible Raman shift and the surface excesses of the different ionic species.A theoretical framework is presented to relate the effect of the applied potential on the Raman shift and its correlation with the surface ionic charge.It is proposed that the Raman shift is governed by the interaction of solvated cations with graphite promoted by polarization conditions.It is the first time that a comparative study on different aqueous electrolyte pH and cation ion size has been performed tracking the Raman spectra change under dynamic polarization conditions and contrasting with compre-hensive electrochemistry and dynamic molecular simulations studies.This study shines lights onto the charge-storage mechanism with evidence of Kohn anomaly reduction in the carbon electrode during the reversible adsorption/desorption and insertion/extraction of ionic species.