In this study, the $PPy/CLO_4$ and PPy/PVS composite electrodes were prepared at various polymerization potential by incorporating electrolyte anions of different anion size during constant potential polymerization. The reulting Polypyrrole surfaces were inspected by SEM, and their electrochemical Properties were investigated with CV and ac impedance method. The results of electrochemical analysis were suggested that anion for $PPy/CLO_4$ electrode and cation fir PPy/PVS electrode were transferred during redox reaction. As constant potential of polymerization was increased, the charge transfer resistance of $PPy/CLO_4$ and PPy/PVS was decreased and the electric double layer capacitances of $PPy/CLO_4$ was higher than that of PPy/PVS. The change of PPy/PVS surface was relatively smaller than that of $PPy/CLO_4$ according to electropolymerization potential.