Streaming potential measurements across charged membranes separating two equal solutions have been carried out. Two cation-exchange membranes with different cross-linked and swelling properties (Ionics and Nafion membranes) and methanol-water electrolyte solutions of KCl have been used in the experiments. The obtained results show that the streaming potential is higher for the Ionics membrane and that the values depend on the methanol content of the solutions. A different behavior is found in the dependence of the streaming potential on the methanol percentage for each membrane. The study of the relaxation times in the decay of electrokinetic steady states of streaming potential has been carried out from the time dependence of the streaming potential when the pressure difference through the membrane is suppressed. The results show the existence of two different parts or partial relaxations, mechanical and electric. A different behavior of the mechanical relaxation time with the methanol percentage has been found for the two membranes, but any significant difference between their electric relaxation times. These differences have been explained in terms of the different degree of swelling of the membranes used. (c) 2005 Elsevier Inc. All rights reserved.