The potential of monoethanolamine (MEA) as an extractive solvent for extractive distillation and liquid extraction was assessed. The systems studied were n-hexane + benzene, cyclohexane + ethanol, and acetone + methanol binary azeotropic systems with MEA as the solvent. Sub-atmospheric vapor-liquid equilibrium data were determined for all the systems with various amounts of MEA in the still feed. Ternary liquid-liquid equilibrium data were determined for the cyclohexane + ethanol + MEA system at 298.15 K and 1 atm. An equivolatility curve map was determined for the acetone + methanol + MEA system at 67.58 kPa. Results show that MEA cannot be used in extractive distillation for the n-hexane + benzene system. A combination of extractive distillation and liquid extraction with MEA as the solvent can be used to obtain pure cyclohexane and pure ethanol from a mixture. MEA works well as a solvent for the extractive distillation of acetone + methanol systems.