A method for the synthesis of anion-exchange membranes by the grafting of ethylenediamine (EDA), diethylenetriamine (DETA) or pentaethylenehexamine (PEHA) onto poly(vinyl chloride) (PVC) film has been presented. The chemical structure was determined by means of Fourier Transform Infrared Spectroscopy (FTIR) and the membranes were characterized by ion-exchange capacity, chloride and nitrogen contents, water regain and surface energetics. The obtained membranes were evaluated in the Donnan dialysis (DD) of hexavalent chromium solutions. Among the membranes, those modified with EDA and DETA showed the best separation features: high flux and high recovery factor (RF). The highest degree of recovery was observed for membranes prepared by the casting of PVC solution in (THF), followed by grafting EDA.