Doping mediators (soluble redox compounds) in polymer electrolyte contained in the porous electrodes is an effective method to increase the capacitance of supercapacitors. Mediators not only provide additional capacitance but also ions to electrolyte. The total capacity of a supercapacitor is dominated by the minor of the electrode capacity and the number of ions in electrolyte. In this research, we focused on revealing the effect of on the extra ions provided by the mediators during the charge/discharge processes. Two types of supercapacitors were fabricated. For the first type, the active electrode material consisted of 50 wt% mediators (in solid state) and 50 wt% high specific surface area active carbon (AC). For the other type of supercapacitor, the active electrode material consisted of AC only. Acetonitrile was used as liquid phase for both types. Under this circumstance, ions are provided by mediator only. The calculation of specific current was based on total weight of two electrodes and cyclic voltammetry (CV) curves. As shown in Figure 1, supercapacitor (a) (AC only) is unable to store any charges and energy without the ions in the solution. However, supercapacitor (b) can store ten times more energy with the mediator enhancement. In this situation, we can consider mediators as ‘charge harbor’. They can release ions into the liquid phase. These ions then participate in formation of electric double layers (EDLs) on AC. This capability of providing ions into the liquid phase can increase capacity of supercapacitor. CVs (b) and (c) also indicate that different mediators are different in the kinetics of providing ions. Taking supercapacitor (b) as an example, when we charge the supercapacitor, the K₂CuFe(CN)₆ can release K⁺ cation into the liquid phase and [CuFe(CN)₆]^- will still be hold on the solid phase because of the electrostatic force. On the other hand, we can use VOSO₄ as a mediator too. V⁴⁺ can be reduced and releases SO₄^2- anion. Thus, it is preferred to use K₂CuFe(CN)₆  in the positive electrode while use VOSO₄ in the negative electrode. An series of mediators were evaluated using the same method.