Sustainable　chemistry　principles　underscore　the　pivotal　role　of　solvent-free　processes　in　the　fabrication　of　anion　exchange　membranes　(AEMs).　This　study　presents　an　eco-friendly,　solvent-free　approach　for　AEM　preparation　via　photopolymerization,　utilizing　4-vinylpyridine　as　the　monomer　and　divinylbenzene　as　the　crosslinking　agent.　The　polymerization,　conducted　at　ambient　temperature　and　completed　within　20　min,　was　followed　by　post-polymerization　N-alkylation　with　ethyl　bromide　to　introduce　pyridinium　groups.　The　precise　modulation　of　crosslinking　and　N-alkylation　levels　enabled　meticulous　control　over　the　membranes＇　intrinsic　chemical　properties　and　their　functional　effectiveness　in　electrodialysis　desalination.　The　optimal　membrane＇s　area　resistance　was　recorded　at　1.09　Ω　cm2,　while　its　transport　number　reached　0.965,　outperforming　the　commercial　AMV　AEM　in　desalination　efficacy.　This　work　underscores　the　promise　of　solvent-free　photopolymerization　as　a　sustainable,　high-performance　strategy　for　fabricating　AEMs,　providing　substantial　advancements　in　both　environmental　sustainability　and　electrodialysis　desalination　performance.　©　2025　Elsevier　B.V.