Liquid-liquid equilibria and separation factors for the systems m-cresol + o-toluonitrile + hexane + water + (glycerol or triethylene glycol) have been determined at 313.15 K in order to evaluate their suitability in separating m-cresol from o-toluonitrile. The effects of parameters such as the type of high-boiling solvent, solvent ratios, antisolvent ratios, and water to high-boiling solvent ratios on the separation of m-cresol from o-toluonitrile were investigated. These are illustrated on the basis of percentage of feed o-toluonitrile remaining in the high-boiling solvent phase and percentage recovery of m-cresol. From the experimental results it was concluded that triethylene glycol is more suitable for the proposed separation than glycerol.