In this study, octahedral crystal MIL101(Cr) with a uniform size of similar to 400 nm is synthesized via hydrothermal reaction. It is then functionalized with sulfonic acid groups by concentrated sulfuric acid and trifluoromethanesulfonic anhydride in nitromethane. The sulfonated MIL101(Cr) are homogeneously incorporated into sulfonated poly(ether ether ketone) (SPEEK) matrix to prepare hybrid membranes. The performances of hybrid membranes are evaluated by proton conductivity, methanol permeability, water uptake and swelling property, and thermal stability. The methanol permeability increased slightly from 6.12 x 10(-7) to 7.39 x 10(-7) cm(2) s(-1) with the filler contents increasing from 0 to 10 wt. %. However, the proton conductivity of the hybrid membranes increased significantly. The proton conductivity is increased up to 0.306 S cm(-1) at 75 degrees C and 100% RH, which is 96.2% higher than that of pristine membranes (0.156 S cm(-1)). The increment of proton conductivity is attributed to the following multiple functionalities of the sulfonated MIL101(Cr) in hybrid membranes: i) providing sulfonic acid groups as facile proton hopping sites; ii) forming additional proton-transport pathways at the interfaces of polymer and MOFs; iii) constructing hydrogen-bonded networks for proton conduction via OH provided by the hydrolysis of coordinatively unsaturated metal sites. (C) 2014 Elsevier B.V. All rights reserved.