The nucleofugality of dimethyl sulfide was measured in solvent mixtures containing ionic liquids. The first-order rate constants of the solvolysis of sulfonium salts were determined in mixtures containing different proportions of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide in ethanol, representing the first report on the solvolysis of a charged species in an ionic liquid. Temperature-dependent kinetic studies allowed determination of activation parameters and rationalization of observed solvent effects in different ionic liquid mixtures. From the solvolysis data, the nucleofugality of dimethyl sulfide in different proportions of this ionic liquid in ethanol was determined. Further, the nucleofugality of dimethyl sulfide was determined in mixtures containing high proportions of each of seven other ionic liquids in ethanol. These data allowed quantification of the effects of varying both the amount of ionic liquid present and on changing the components of the ionic liquid on the nucleofugality of dimethyl sulfide. The ionic liquid mixtures were shown to affect the nucleofugality of this nucleofuge in a different manner to the previously studied monatomic charged nucleofuges, owing to different microscopic interactions in solution. This work highlighted the necessity of considering electrofuges with an appropriate range of electrofugality values along with the importance of the nucleofuge-specific sensitivity parameter.