Ionic　liquids　(ILs)　have　been　proposed　as　potential　environmentally　friendly　and　efficient　solvents　for　gas　absorption　and　purification.　In　this　study,　we　propose　the　utilization　of　ILs　for　vinyl　chloride　(VC)　capture.　The　structural　effects,　including　the　cationic　skeleton　and　alkyl　chain　length　on　the　cation,　as　well　as　the　anionic　structures　such　as　alkyl　chain　length　for　phosphate　and　sulfate　anions　and　the　fluorination　effect,　were　systematically　investigated　at　a　microscopic　level　using　COSMO-RS　mode　and　quantum　chemical　calculations.　ILs　screening　results　reveal　that　noncyclic　cationic　skeletons　with　long　alkyl　chains　on　both　cations　and　phosphate/　sulfate-based　anions,　without　fluorinated　derivatives,　are　favorable　for　VC　absorption　due　to　their　large　fractional　free　volume　and　nonpolar　nature.　Both　the　anion　and　cation　contribute　to　the　absorption　process;　however,　the　anion　effect　plays　a　more　significant　role.　The　interaction　between　VC　and　the　cation　is　mainly　governed　by　van　der　Waals　forces,　while　both　hydrogen　bonding　interactions　and　van　der　Waals　forces　exist　between　VC　and　the　anion.