A　series　of　bisimidazolium　tungstate　ionic　liquids　were　synthesized　and　applied　to　catalyze　the　reaction　of　ethylene　carbonate　(EC)　with　alcohols.　A　detailed　investigation　was　carried　out　on　the　relationship　between　catalyst　structures　and　catalytic　activities.　The　result　showed　that　1-butyl-3-methyl-bisimidazolium　tungstate　([Bmim]2WO4)　containing　double　C2–H　in　bisimidazolium　and　WO42−　had　more　effectively　catalytic　performance　than　other　bisimidazolium　tungstate　and　conventional　imidazolium　salt　(OAc−,　Cl−,　Br−).　Under　the　optimized　conditions　of　1:15　molar　ratio　of　EC　and　ethanol,　5 mol%　[Bmim]2WO4,　85 °C　and　0.5 h,　the　yield　of　diethyl　carbonate　(DEC)　was　nearly　100%.　The　detailed　DFT　calculations　and　NMR　spectroscopy　indicated　that　the　high　catalytic　activity　of　[Bmim]2WO4　was　not　only　because　the　strong　nucleophilic　ability　of　WO42−　could　activate　ethanol,　but　also　the　special　structure　of　double　C2–H　in　bisimidazolium　could　cooperatively　activate　EC.　The　reaction　was　catalyzed　by　synergistic　effect　in　double　C2–H　and　WO42−　of　[Bmim]2WO4.　In　addition,　[Bmim]2WO4　could　be　used　seven　times　without　significant　loss　of　catalytic　activity.　Graphical　Abstract:　[Figure　not　available:　see　fulltext.]　©　2022,　The　Author(s),　under　exclusive　licence　to　Springer　Science+Business　Media,　LLC,　part　of　Springer　Nature.