Aromatic　hydrocarbons　are　considered　a　class　of　extremely　hazardous　atmospheric　pollutants　of　volatile　organic　compounds　(VOCs).　Toluene　is　a　typical　aromatic　VOC　representative,　and　its　removal　has　a　significant　contribution　to　the　treatment　of　air　pollution.　In　this　work,　two　imidazolium-based　ionic　liquids　(ILs)　introduced　into　pi-electron　donors,　[PhCH2MIM][Tf2N]　and　[AMIM][Tf2N],　were　designed　and　synthesized　to　capture　toluene　for　the　first　time,　and　it　was　found　that　their　performances　of　toluene　capture　are　obviously　enhanced　when　compared　with　the　common　IL　[EMIM][Tf2N]　in　a　continuous　experiment.　In　particular,　[PhCH2MIM][Tf2N]　presents　the　most　excellent　capture　capacity　among　all　ILs,　and　the　toluene　content　of　the　outlet　gas　is　decreased　as　2.2　ppm　at　ambient　temperature　and　pressure　with　fresh　[PhCH2MIM][Tf2N]　as　an　absorbent.　Moreover,　the　microscopic　mechanisms　regarding　the　significant　improvement　for　performance　of　toluene　capture　were　systematically　investigated　and　clarified　from　the　multiple　insights　of　quantum　chemistry　(QC)　and　molecular　dynamics　(MD).　Overall,　the　proposed　ILs　were　considered　as　promising　green　absorbents　to　achieve　highly　efficient　toluene　capture,　and　the　design　concept　could　also　provide　valuable　guidance　to　develop　new　green　and　efficient　task-specific　separation　agents　for　capturing　other　aromatic　VOCs.