P2ClAn/PVDF composite membranes were prepared utilizing cation-exchange groups in the PVDF (polyvinylidenefluoride) membrane matrix by casting method. The poly(2-chloroaniline) (P2ClAn) was chemically synthesized with different dopant anions such as o-aminobenzene sulfonic acid (ABS) and sodium dodecyl sulfate (SDS). P2ClAn/PVDF membranes were extensively characterized for their surface morphology, thickness, ion-exchange capacity, SEM, AFM, and FTIR-ATR measurements. The SEM, AFM and FTIR-ATR pictures, comparing the original PVDF membrane support sheet to P2ClAn/PVDF composite membranes, indicate that the morphologies of the membranes are different. The membrane potential measurements were performed in various electrolyte solutions in order to observe the selectivity and stability of these membranes at different pHs. The P2ClAn/PVDF cation-exchange membranes were then used for the removal of chromium(III) and copper(II) ions from aqueous solution with Donnan dialysis. The flux values (J) of chromium(III) and copper(II) were obtained. The flux value of copper(II) ion was higher than chromium(III) for all of composite membranes because of the hydration volume.