The present work aims to study the influence of the solvents monoethanolamine (MEA), N-methyl-2-pyrrolidone (NMP), and monoethylene glycol (MEG) on the subsequent extractive distillation of a benzenecyclohexenecyclohexane mixture. Process simulations were carried out using the Aspen Plus software, considering a mixture composition obtained from previous catalytic tests for benzene hydrogenation in the liquid phase. The adopted production of cyclohexene, the main product of interest, was based on the capacity of a large chemical company in Sao Paulo state (Brazil). The results show that MEA is efficient only to separate benzene, whereas with the use of NMP or MEG all components are separated with high purity. Monoethylene glycol is a more advantageous solvent for this extractive distillation since its use leads to more practicable operating conditions and lower energy consumption, besides being a less expensive and biodegradable compound.