Trivalent chromium Cr(III) in wastewaters produced by leather tanning processes must be treated before discharge in the environment. Electrodialysis was studied for this application. Cr(III) ion is separated from sodium ion by using modified cation-exchange membranes. The membrane modification consists of a polyethylenimine layer electrodeposited on the membrane surface. This layer is positively charged in acidic media and repels multivalent ions while monovalent ions cross the membrane. The modified membrane in this study was a Nafion (R) 324 membrane. The transfer of chromium, sodium, calcium, magnesium, chloride and sulphate ions from a mixture was investigated. The pH must be regulated in order to avoid chromium hydroxide precipitation in the dilute chamber. The behaviour of sulphate chloride system is unusual for the AMX membrane. Adsorption of PEI on the membrane surface is assumed to explain this behaviour. The overall current efficiency was close to 96-98% for cations and anions. (c) 2006 Elsevier B.V. All rights reserved.