In this study, heterogeneous ion exchange membranes were prepared by casting method with various mixing ratios of PPO ion-selective solution and ion exchange resin. Then heterogeneous bipolar membranes were prepared by using this. The water content of heterogeneous cation and anion exchange membranes were 60~80% respectively, the ion exchange capacity was 2.81~3.26 meq/g, 2.31~2.74 meq/g and electrical resistances were 1.65~1.45 Ω·cm2 and 1.55 ~1.05 Ω·cm2. The tensile strength of heterogeneous bipolar membrane was lower than that of PPO resin before functionalization (700 Kgf/cm2). The tensile strength of heterogeneous bipolar membrane with catalyst layer was lower than that of non-catalytic heterogeneous bipolar membrane. The water splitting voltage of the heterogeneous bipolar membrane with catalyst layer was low and stable at a minimum of 1.7~1.8 V, maximum 3.9~4.0 V, and the water splitting voltage of the non-catalytic heterogeneous bipolar membrane was constant at 3.8~4.0 V.