Capture　and　recovery　of　ammonia　(NH3)　from　industrial　exhaust　is　a　win-win　strategy　for　resource　utilization　and　contaminants　control.　[CAM][Cl]@MIL-101(Cr)　composite　designed　and　prepared　based　on　ionic　liquids　(ILs,　carbamide　chloride:　[CAM][Cl])　and　metal-organic　frameworks　(MOFs,　MIL-101(Cr))　has　exhibited　potentials　for　NH3　capture　capacity　(11.61　mmol/g)　and　NH3/CO2　separation　(SNH3/CO2　=　3,266).　The　selectivity　is　3.13　times　as　high　as　that　of　the　parent　MIL-101(Cr)　and　higher　than　the　highest　values　in　literature.　Not　only　that,　the　breakthrough　experiment　of　NH3/CO2　mixture　further　proves　that　high-purity　NH3　can　be　obtained　in　one　step　(Separation　Factor　is　about　1518).　Such　excellent　performance　originates　from　the　synergistic　effect　of　various　types　of　interaction　sites　and　adsorption　spaces.　The　theoretical　calculation　reveals　that　the　hydrogen　bond　(HB)　interaction　between　ILs　and　NH3　plays　a　greatly　significant　role　in　enhancing　NH3　adsorption　and　separation　selectivity　of　NH3/CO2　for　the　composite.　In　addition,　the　composite　exhibits　good　structural　stability　and　regenerability.　More　importantly,　the　novel　design-strategy　can　avoid　the　challenge　for　precise　control　of　the　microstructure　and　channel　environment　of　adsorbents,　which　is　beneficial　to　the　development　of　novel　materials.