For the first time, the performance of six new trigeminal tricationic ionic liquids (TTILs) was evaluated for different separation problems. The different selectivity and capacity values obtained on these TTILs show that the choice of the anion, the cation, and the functionalized chain plays an important role on the efficiency of the separation process. It was found that two TTILs have the highest selectivity and capacity observed up to now for numerous separation problems such as the separation of aromatics (or alcohols or thiophene) from aliphatic hydrocarbons. The solvation characteristics of this class of ionic liquids were also evaluated using linear solvation energy relationships (LSERs). Results indicate that TTILs and monocationic ionic liquids have similar solvation properties.