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Ion-exchange membranes (IEMs) are a core component that greatly affects the performance of electrochemical energy conversion processes such as reverse electrodialysis (RED) and all-vanadium redox flow battery (VRFB). The IEMs used in electrochemical energy conversion processes require low mass transfer resistance, high permselectivity, excellent durability, and also need to be inexpensive to manufacture. Therefore, in this study, thin-reinforced anion-exchange membranes with excellent physical and chemical stabilities were developed by filling a polyethylene porous substrate with functional monomers, and through in situ polymerization and post-treatments. In particular, the thin-reinforced membranes were made to have a high ion-exchange capacity and a limited degree of swelling at the same time through a double cross-linking reaction. The prepared membranes were shown to possess both strong tensile strength (>120 MPa) and low electrical resistance (2). As a result of applying them to RED and VRFB, the performances were shown to be superior to those of the commercial membrane (AMX, Astom Corp., Japan) in the optimal composition. In addition, the prepared membranes were found to have high oxidation stability, enough for practical applications.