As a fundamental research on the optimization of electrolyte composition in practical electrochemical capacitor device, double-layer capacitance at Glassy Carbon (GC) and Boron-doped Diamond (BDD), as typical smooth-surface carbon electrodes, has been studied as a function of the electrolyte composition in organic media. Specific capacitance (differential capacitance: Fcm−2) determined by an AC impedance method, in which no contribution of mass-transport effects is included, corresponded well to integrated capacitance evaluated by conventional cyclic voltammetry. The specific capacitance at the GC electrode varied with polarized potential and showed clear PZC (potential of zero charge), while the potential dependence of the capacitance at BDD was very small. The effects of the solvent and the electrolytic salt on the capacitance behavior were common for both electrodes. That is, the sizes of the solvent molecule and the electrolytic ion (cation) strongly affected the capacitance at these smooth-surface carbon electrodes.