Free radical attack on Proton exchange membranes (PEM) is detrimental to the long-term durability of proton exchange membrane fuel cells (PEMFCs), and although state-of-the-art cerium-based antioxidants defend against free radical attack, potentially impairing the proton conductivity of PEM limits their more comprehensive application. To break the "trade-off" between the durability and proton conductivity of PEM, a functionalized cerium oxide (CeO 2 @Ph-PEI) composite with a synergistic enhancement of durability and proton conductivity has been synthesized induced by phosphate-grafted polyethyleneimine (Ph-PEI). Owing to the strong adsorption of phosphate groups on transition metal hydroxides/oxides, Ph-PEI was rmly anchored on the particle surface during the transition from sol-gel to oxide, which suppressed the further aggregation of CeO 2 nanoparticles and thus retained abundant active sites for free radical scavenging. Moreover, due to the extra proton transport sites in the anchored Ph-PEI functional shells, the hybrid membrane fabricated with CeO 2 @Ph-PEI as the antioxidant additive exhibited a high proton conductivity up to 0.242 S cm − 1 , which was approximately 1.32 times higher than that of the unmodi ed CeO 2 -based hybrid membrane. Consequently, CeO 2 @Ph-PEI-based PEMs exhibited an OCV decay rate of 0.32 mV h − 1 , a maximum power density of 1.19 W cm − 2 , an H 2 crossover value of 2.12 mA cm − 2 , and thickness retention (93.7%) after 200 hours of accelerated degradation testing. This strategy synergistically improves the proton conductivity of PEMs and the lifetime of PEMFCs through CeO 2 functionalization, providing a promising solution for next-generation fuel cell-based energy storage techniques.