The activity coefficients at infinite dilution, γ13∞, for 62 solutes, including alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, water, thiophene, ethers, ketones, acetonitrile, pyridine and 1-nitropropane in the ionic liquid 1-butyl-1-methylpyrrolidinium tricyanomethanide, [BMPYR][TCM] were determined by gas–liquid chromatography at six temperatures over the range of (318.15 to 368.15)K. The partial molar excess Gibbs free energy, ΔG1E∞, enthalpy ΔH1E∞, and entropy term TrefΔS1E,∞ at infinite dilution were calculated from the experimental γ13∞ values obtained over the temperature range. The densities of [BMPYR][TCM] were measured within temperature range from 318.15K to 368.15K. The gas–liquid partition coefficients, KL were calculated for all solutes. The values of selectivity for few separation problems as hexane/benzene, cyclohexane/benzene, heptane/thiophene were calculated from γ13∞ and compared to literature values for N-methyl-2-pyrrolidinone (NMP), sulfolane, and other ionic liquids based on [BMPYR]+ cation. In comparison with the former measured ILs, [BMPYR][TCM] present quite high selectivity for the separation of aromatic hydrocarbons and aliphatics hydrocarbons, an average capacity for benzene. The data presented here shows that [BMPYR][TCM] ionic liquid can be used as an alternative solvent for the separation of thiophene from the aliphatic hydrocarbons.