[Display omitted] • The simultaneous screening of multiple ionic liquids under controlled environment. • In situ ATR-FTIR spectroscopic imaging was used in high-throughput analysis of ILs. • ATR-FTIR imaging provides a platform for the simultaneous screening of multiple ILs. • Array of ILs was studied for sorption separately of water vapour and toluene vapour. • The information about ILs was obtained rapidly, quantitatively and simultaneously. In situ characterisation of ionic liquids under a controlled environment has been performed in a high throughput manner using macro ATR-FTIR spectroscopic imaging. 14 different ionic liquids with cations 1-butyl-3-methylimidazolium ([C 4 mim]), 1-butyl-2,3-dimethylimidazolium ([C 4 mmim]) and 1-butyl-3-methylpyrrolidinium ([C 4 C 1 pyrr]) and anions hexafluorophosphate ([PF 6 ]), tetrafluoroborate ([BF 4 ]), bis(trifluoromethylsulfonyl)imide ([NTf 2 ]), perchlorate ([ClO 4 ]), trifluoromethanesulfonate ([CF 3 SO 3 ]), nitrate ([NO 3 ]), methanesulfonate ([CH 3 SO 3 ]) and trifluoroacetate ([TA]) were studied. The ionic liquids were deposited onto the measuring surface of the ATR crystal in the corresponding accessory hosted in the FTIR imaging system. Then these samples were exposed to a controlled environment of toluene and water vapour and spectra acquired simultaneously. Changing the structure of the cation head group from [C 4 mim] to [C 4 mmim] or [C 4 C 1 pyrr] only had a small effect on the toluene absorption while increasing the length of the alkyl chain of the cation (e.g. [C 10 mim]) has shown a significant increase in toluene absorption. The ionic liquids with the anion [NTf 2 ] were found to absorb the highest amount of toluene followed by [CF 3 SO 3 ], then [PF 6 ], [ClO 4 ], [NO 3 ] and [TA], and the lowest amount of toluene was absorbed in ionic liquids with [BF 4 ] or [CH 3 SO 3 ] anions. The amount of water absorbed increases in the order: [C 4 mim][CH 3 SO 3 ] > [C 4 mim][TA] > [C 4 mim][NO 3 ] > [C 4 mim][CF 3 SO 3 ] > [C 4 mim][ClO 4 ] ~ [C 4 mim][BF 4 ] ~ [C 4 mmim][BF 4 ] > [C 10 mim][BF 4 ] > [C 4 mim][PF 6 ] ~ [C 4 mmim][PF 6 ] > [C 4 mim][NTf 2 ] ~ [C 4 mmim][NTf 2 ] ~ [C 4 C 1 pyrr][NTf 2 ]. This work has demonstrated that spectroscopic imaging provides a platform for the simultaneous screening of multiple ionic liquids in situ, when under controlled environments. [ABSTRACT FROM AUTHOR]