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　Omega　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.