High porous poly(hydroxyethyl acrylate-co-acrylonitrile) [P(HEA-AN)] membranes were prepared by a phase inversion method. Porous polymer electrolytes are prepared by soaking the porous membranes in the electrolyte solution. The ionic conductivity of the porous polymer electrolytes was found to be as high as 3.66 x 10(-3) S cm(-1). The membrane structure changed with the different processing conditions. With increasing mole ratio of AN in the copolymer, the cross-sectional structure of the membrane changes from finger-like to honeycomb-like and ionic conductivity of porous polymer electrolytes is improved. As the polymer concentration increases, the pore diameter of porous membrane decreases and ionic conductivity of porous polymer electrolyte is improved obviously. (c) 2007 Elsevier B.V. All rights reserved.