To enhance the anhydrous proton conductivities of proton exchange membranes, we report here the incorporation of H3PO4 into three-dimensional (3D) framework of polyacrylamide-graft-starch (PAAm-g-starch) hydrogel materials using extraordinary absorption of hydrogels to H3PO4 aqueous solution. Intrinsic microporous structure can close to seal H3PO4 molecules in the interconnected 3D frameworks of PAAm-g-starch after suffering from dehydration. The hydrogel membranes are thoroughly characterized by morphology observation, thermal stability, swelling kinetics, proton-conducting performances as well as electrochemical behaviors. The results show that the H3PO4 loadings and therefore the proton conductivities of the hydrogel membranes are dramatically enhanced by employing PAAm-g-starch matrix. H3PO4 loading of 88.68 wt% and an anhydrous proton conductivity as high as 0.046 S cm(-1) at 180 degrees C are recorded. A fuel cell using a thick membrane shows a peak power density of 517 mW cm(-2) at 180 degrees C by feeding with H-2/O-2 streams. The high H3PO4 loading, reasonable proton conductivity in combination with simple preparation, low cost and scalable matrix demonstrates the potential use of PAAm-g-starch hydrogel membranes in high-temperature proton exchange membrane fuel cells. Copyright 0 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.