Instead of modification of pre-existing polymers, a new route of preparation of polyelectrolyte OH- conductive membranes via copolymerization of selected functional monomers was reported in this study. A random copolymer of poly(methyl methacrylate-co-butyl acrylate-co-vinylbenzyl chloride) was synthesized via copolymerization, which was followed by quaternization and membrane casting. The intrinsic OH- conductivity of the free-standing polyelectrolyte membranes can reach 8.2 x 10(-3) S cm(-1) at 80 degrees C. The alkaline fuel cells using copolymer polyelectrolytes demonstrated the feasibility of the preparation concept of these membranes. (C) 2010 Elsevier B.V. All rights reserved.