Dimethyl　carbonate　(DMC)　is　a　crucial　chemical　raw　material　widely　used　in　organic　synthesis,　lithium-ion　battery　electrolytes,　and　various　other　fields.　The　current　primary　industrial　process　employs　a　conventional　sodium　methoxide　basic　catalyst　to　produce　DMC　through　the　transesterification　reaction　between　vinyl　carbonate　and　methanol.　However,　the　utilization　of　this　catalyst　presents　several　challenges　during　the　process,　including　equipment　corrosion,　the　generation　of　solid　waste,　susceptibility　to　deactivation,　and　complexities　in　separation　and　recovery.　To　address　these　limitations,　a　series　of　alkaline　poly(ionic　liquid)s,　i.e.　[DVBPIL][PHO],　[DVCPIL][PHO],　and　[TBVPIL][PHO],　with　different　cross-linking　degrees　and　structures,　were　synthesized　through　the　construction　of　cross-linked　polymeric　monomers　and　functionalization.　These　poly(ionic　liquid)s　exhibit　cross-linked　structures　and　controllable　cationic　and　anionic　characteristics.　Research　was　conducted　to　investigate　the　effect　of　the　cross-linking　degree　and　structure　on　the　catalytic　performance　of　transesterification　in　synthesizing　DMC.　It　was　discovered　that　the　appropriate　cross-linking　degree　and　structure　of　the　[DVCPIL][PHO]　catalyst　resulted　in　a　DMC　yield　of　up　to　80.6%.　Furthermore,　this　catalyst　material　exhibited　good　stability,　maintaining　its　catalytic　activity　after　repeated　use　five　times　without　significant　changes.　The　results　of　this　study　demonstrate　the　potential　for　using　alkaline　poly(ionic　liquid)s　as　a　highly　efficient　and　sustainable　alternative　to　traditional　catalysts　for　the　transesterification　synthesis　of　DMC.　©　2024　The　Chemical　Industry　and　Engineering　Society　of　China,　and　Chemical　Industry　Press　Co.,　Ltd