Blend membranes were obtained by solution casting from poly(vinylidene fluoride) (PVDF) and sulfonated poly(ether ether ketone) (SPEEK) in N,N'-dimethylacetamide (DMAc). DSC and XRD were used to characterize the structure of the blend membranes. The effect of PVDF content on the membrane properties was investigated. The methanol permeability, water uptake and the swelling ratio of blend membranes decreased with the increase of PVDF content. Though the proton conductivity decreased upon the addition of PVDF, they were still comparable to that of Nafion (R) 117 membrane. Higher selectivities were also found for most blend membranes in comparison with Nafion (R) 117 membrane. The effect of methanol concentration on solution uptake, swelling ratio and methanol permeability of the blend membranes was also studied. (c) 2006 Elsevier Ltd. All rights reserved.