In this study, we prepared porous cation exchange membrane using polystyrene such as, EPS (expanded polystyrene), SAN (styrene acrylonitrile copolymer) and HIPS (high impactive polystyrene). These polystyrenes were sulfonated by acetyl sulfate to make porous cation exchange membrane such as, SEPS, SSAN, SHIPS. SEM was employed to confirm porous structure of membrane, and IR spectroscopy was used to confirm sulfonation rate of ion exchange membrane. Water and methanol content were also increased with amount of sulfuric acid in reactants. SSAN-20 showed the highest value in water and methanol content. Fixed ion concentration and conductivity was also increased with an amount of sulfuric acid in reactants. Methanol permeability for SEPS-20, SSAN-20, SHIPS-20 was found to be $1.326;{ imes};10^{-5};cm^2/s$, $1.527;{ imes};10^{-5};cm^2/s$ and $1.096;{ imes};10^{-5};cm^2/s$ respectively. From the result of electrodialysis experiment in 0.03 M $Pb(NO_3)_2$ aqueous solution, anion exclusion and cation selection effects were confirmed.