Heterocyclic compounds are known as proton transfer species for anhydrous polymer electrolyte membrane (PEM), for which efficient proton conductivity at high operating temperature has yet to be found. The present work proposes an approach to enhance the proton transfer of the membrane by combining the concept of proton donor and acceptor with an ordered structure, i.e. layer-by-layer (LbL). By simply applying poly(acrylic acid) (PAA) as a polymeric proton donor and benzimidazole (BIm) conjugated on branching poly(ethyleneimine) as a polymeric proton acceptor and alternately coating the sulfonated poly(ether ether ketone) (SPEEK), a LbL membrane can be obtained. The proton transfer can be fine-tuned by the number of bilayers, and at that time, the 20-bilayered SPEEK/BIm-PEI/PAA is an optimal condition, which achieves a balance between the hydrogen bond and chain mobility under LbL packing that allows a 1.5 higher order of magnitude conductivity than an as-prepared SPEEK membrane even at a high operating temperature range (90 -170 degrees C). The present work, for the first time, shows how a simple LbL technique is practical constructing high-ordered structure of proton donor and acceptor species on the membrane surface for the efficient proton transfer in a PEM. Copyright (c) 2016, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.