Carbon dioxide has been shown to be an effective antisolvent gas for separating organic compounds from ionic liquids (ILs) by inducing a liquid–vapour to liquid–liquid–vapour transition. Using carbon dioxide, toluene can be separated from imidazolium, phosphonium and pyridinum cation-based ILs with the bis(trifluoromethylsulfonyl)imide anion, which is relatively hydrophobic and has a high toluene solubility. A new IL with relatively low viscosity is tested here for the same toluene separation process: 1- n -butylthiolanium bis(trifluoromethylsulfonyl)imide. Carbon dioxide solubility in binary and ternary systems containing toluene and 1- n -butylthiolanium bis(trifluoromethylsulfonyl)imide is measured at 298.15 and 313.15 K up to 7.4 MPa. Solubility behaviour in this IL is similar to imidazolium-based ILs with the same anion. However, phase split pressures are lower when 1- n -butylthiolanium bis (trifluoromethylsulfonyl)imide is used instead of 1- n -hexyl-3-methylimidazolium bis(trifluoromethylsu- lfonyl)imide at the same conditions of temperature and initial composition of toluene in the IL. Solubility data are modelled with the conductor-like screening model for real solvents combined with the Soave–Redlich–Kwong equation of state, which provides good qualitative results.