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We herein report a new class of high-temperature proton exchange membranes comprised of poly(acrylic acid-graft-hexadecyltrimethylammonium bromide) (PAA-g-CTAB) or poly(acrylic acid)-graft-poly(ethylene glycol) (PAA-g-PEG) hydrophobic hydrogel caged H3PO4. The membranes exhibit reasonable proton conductivity, enhanced H3PO4 retention ability and low solubility in water, making them promising as potential high performance and robust electrolytes for high-temperature proton exchange membrane fuel cells. Although the proton conductivity is still lower than that of H3PO4 doped PBI membranes, the new concept provides a different approach to proton exchange membranes for acid retention.