The tie-line composition for the ternary systems of [EMIM][EtSO4](1)+thiophene(2)/benzothiophene(2)+n-hexadecane(3), and [EMIM][MeSO3](1)+thiophene(2)/benzothiophene(2)+n-hexadecane(3) is experimentally determined at 298.15K. This measured LLE data was compared and correlated with COSMO-RS model, NRTL and UNIQUAC models. The good fitness of experimental data with model values was calculated by RMSD and a good agreement was obtained. Besides, the extraction capability of [EMIM][EtSO4] and [EMIM][MeSO3] towards sulphur-containing compounds was also investigated with respect to distribution coefficient and selectivity. The consistency of tie-line data was ascertained by applying the Othmer–Tobias and Hand equations.