Nowadays, extraction of aromatics from aromatic/aliphatic mixtures is being investigated using cyano-based ionic liquids (as) as a new green alternative to currently used conventional organic extraction solvents, such as sulfolane. In this process, the maximum operation temperature (MOT) of the IL is a decisive property to know. Thus, thermal behavior of ILs is a target issue to study. The MOTs of cyano-based ILs 1-ethyl-3-methylimidazolium dicyanamide ([emim][DCA]), 1-butyl-3-methylimidazolium dicyanamide ([bmim][DCA]), 1-ethyl-3-methylimidazolium thiocyanate ([emim][SCN]), 1-butyl-3-methylimidazolium thiocyanate ([bmim][SCN]), and 1-ethyl-3-methylimidazolium tricyanomethanide ([emim][TCM]) have been determined using dynamic and isothermal thermogravimetric analyses. In addition, specific heats from (296.2 to 372.2) K of all ILs included in this work have been also measured using differential scanning calorimetry (DSC). The MOT for [emim] [TCM] was the highest, whereas the MOT for [emim] [DCA], [bmim][DCA], and [bmim][SCN] were a little lower, the [emim][SCN] MOT being the lowest found. Specific heats of all ILs analyzed were higher than that of sulfolane.