Zirconium glyphosate (ZrG) is a solid proton conductor with layered crystal structure. The inorganic veneer sheets of ZrG are covalently intercalated by glyphosate molecules with carboxylic acid end groups (-COOH). The existence of abundant -COOH groups both inside and on the surface of ZrG provides additional proton-conducting channels facilitating the proton conduction through and around the inorganic crystals. ZrG is incorporated into the sulfonated polyether ether ketone (SPEEK) matrices to prepare proton-conducting hybrid membranes. The conductivity of the hybrid membranes is higher than the pristine SPEEK membrane, and increases with increasing ZrG content. Furthermore, the enhancement of the proton conductivity is more obvious at elevated temperatures. At 25 degrees C, the proton conductivity of the hybrid membrane with 16 wt% ZrG is 1.4 times higher than that of the pristine membrane. When the temperature increases to 55 degrees C, the conductivity of the hybrid membrane with 8 wt% ZrG is more than twice that of the pristine SPEEK membrane. The prolonged and tortuous pathways originated from the incorporation of inorganic crystals lead to reduced methanol permeability. The selectivity of the hybrid membrane is increased by as much as 72% compared to the pristine SPEEK membrane. (C) 2011 Elsevier B.V. All rights reserved.