Introducing ZIF-8 into the PES-cSMM membranes played a pivotal role in the development of proton-conducting pathways and an effective methanol barrier. We employed dry-wet phase inversion techniques to fabricate PES-cSMM, finding that a 3 wt cSMM content yielded optimal results. The resulting PES-cSMM exhibits impressive performance, with a 38 higher selectivity and a 95 greater methanol barrier compared to Nafion® 117. The imidazole-N-H linker in the terminal PES-cSMM/ZIF-8 promotes proton transport through a hydrogen bond chain, while the hydrophobic backbone acts as an effective methanol filter. As a result, PES-cSMM/ZIF-8 boasts a 13-fold higher water uptake than Nafion® 117 and achieves a 99 improvement in methanol sieving performance, a highly promising breakthrough for DMFC systems. Proton conductivity for the PES-cSMM/ZIF-8 immersion membrane reaches 19.5 � 10-3 Scm-1, comparable to Nafion® 117, which is 20.4 � 10-3 Scm-1. The structural flexibility of ZIF-8 within PES-cSMM facilitates efficient proton conduction, while the ZIF-8 cage acts as a robust methanol barrier. Computational analysis revealed covalent bonding within the PES-cSMM system. We characterized the chemical interactions in PES-cSMM/ZIF-8 using topology analysis, specifically the Atom in Molecules/Non-covalent analysis (AIM/NCI) technique. © 2023 Elsevier Inc.