To determine the correlation between surface properties and concentration polarization (CP) behaviors, cation exchange membranes with varying fixed charge densities were prepared and characterized by using several electrochemical analyses such as chronopotentiometry, zeta potential, and current-voltage measurements. Results showed that CP behavior depended mainly on surface charge density. With higher surface charge density, stronger electroconvection was observed, suggesting that an increase in the surface charge density increased the concentration of the counter ions at the membrane surface. As such, the electric field around the membrane surface was strengthened at a current over the limiting current density. Water splitting was also proportional to the surface charge density. This result was consistent with the classical electric field-enhanced water splitting theory, indicating that water splitting increased due to increases in the electric field and prepolarization of water molecules at the membrane-solution interface of the cation-exchange membrane.