In this study, block copolymer ionomers of the cesium salt (20 mol %) of fluorinated polyisoprene-block-sulfonated polystyrene were spin cast into membranes and annealed under an electric field of similar to 40 V/mu m at 130 degrees C for 24 h. The effect of this treatment was a 2.5 times increase in the ionic conductivity as measured by electrochemical impedance spectroscopy, under all humidity conditions measured. This can be attributed to the increased connectivity of the ionic domains of the block copolymers. This E-field alignment technique may thus find application in the fabrication of nanostructured polyelectrolytes with enhanced charge transport capacity. (C) 2011 Elsevier Ltd. All rights reserved.