This study introduces an innovative approach to fabricate well-defined cross-linked proton exchange membranes (PEMs) using radiation-induced reversible addition-fragmentation chain transfer (RAFT)-mediated polymerization on cost-effective ethylene tetrafluoroethylene (ETFE) films. The incorporation of the RAFT mechanism into the cross-linking process significantly enhanced structural homogeneity, providing uninterrupted proton conductivity. Thorough characterizations confirmed the successful grafting of polystyrene (PS) chains onto ETFE films and subsequent sulfonation. Despite a reduction in proton conductivity attributed to restricted chain movements, a notable improvement in chemical stability was observed after cross-linking reactions. Chemical stability of the cross-linked membranes increased approximately 4-fold compared to those synthesized without a cross-linker. The synthesized PEMs with degrees of grafting at 45% and 67% demonstrated superior proton conductivity, outperforming various alternatives, including commercial Nafion samples. Specifically, these cross-linked membranes exhibited promising proton conductivity values of 93.7 and 139.1 mS cm-1, respectively. This work highlights the potential of radiation-induced RAFT-mediated polymerization in carrying out cross-linking reactions as an efficient pathway for designing well-defined high-performance PEMs, offering enhanced homogeneity and conductivity compared to existing literature counterparts.