In this paper, the blend membranes based on sulfonated poly(ether ether ketone) and sulfonated cyclodextrin as the proton conducting membranes for DMFCs usage are prepared and investigated. The incorporation of sulfonated cyclodextrin in SPEEK membranes is evaluated by the characteristic absorptions of FT-IR spectra. Thermal stability and micro-morphology of the blend membranes are determined by thermogravimetry analysis and scanning electron microscope tests. The properties of the blend membranes are investigated such as swelling behavior, methanol permeability and proton conduction as function of the fraction of sulfonated cyclodextrin. The methanol crossover could be suppressed by the incorporation of sulfonated cyclodextrin and the methanol permeability decreases when the methanol concentration increases from 2.5 M to 20 M. Proton conduction is also promoted by the introduction of sulfonated cyclodextrin and the proton conductivity increases with the increase of sulfonated cyclodextrin content. The calculated activation energy for proton conduction of the blend membranes is very low and the maximum value is 4.20 kJ mol(-1), which is much lower than that of Nafion 115 (9.15 kJ mol(-1), measured in our experiments). These data indicate that proton can transport easily through the blend membranes. The selectivity of the blend membranes, a compromise between proton conductivity and methanol permeability, is much higher than that of Nafion 115 at the sulfonated cyclodextrin content above 15 wt.%. The blend membranes with 15, 20, and 25 wt.% of sulfonated cyclodextrin are assembled in the practical DMFCs and their polarization curves with 2.5 M and 8.0 M methanol solution are determined, respectively. The membrane with 20 wt.% sulfonated cyclodextrin reaches the highest power density of 29.52 mW cm(-2) at 120 mA cm(-2) and 8.0 M methanol solution. These results suggest the potential usage of the SPEEK membranes incorporating with sulfonated cyclodextrin in DMFCs. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.