The graphene oxide (GO) sheets are functionalized by histidine molecules and incorporated into sulfonated poly (ether ether ketone) (SPEEK) matrix to fabricate hybrid polymer electrolyte membranes for direct methanol fuel cells (DMFCs). The loading of functionalized GO is varied to investigate its influence on cross-sectional morphology, crystalline structure, polymer chain stiffness, thermal stability and fractional free volume of membrane, etc. The acidic -SO3H groups (proton donors) in SPEEK and basic imidazole groups (proton acceptors) in histidine molecules form acid-base pairs and transport protons synergistically, thus yielding efficient proton channels inside the hybrid membranes. The maximum proton conductivity (at 100% RH) of hybrid membranes is elevated by 30.2% compared with the plain SPEEK membrane at room temperature. The functionalized GO flakes also confer the hybrid membranes low methanol permeability in the range of 1.32-3.91 x 10 (7) CM2 s (1). At the filler content of 4 wt%, the hybrid membrane shows a superior selectivity of 5.14 x 10(5)S s cm 3 and its maximum power density of single DMFC cell (43.0 mW cm (2)) is 80.7% higher than that of plain SPEEK membrane. (C) 2016 Elsevier Ltd. All rights reserved.