Abstract Monoglycerides obtained by glycerolysis of palm stearin can be purified by extraction with aqueous ethanol, a process much less expensive than molecular distillation, which is the method that is commonly used at the industrial level. Liquid–liquid equilibrium data were measured for the six pseudoternary systems involved in the purification of the crude monoglyceride mixture obtained by glycerolysis of palm stearin. These systems are monoglycerides–ethanol–water, diglycerides–ethanol–water, triglycerides–ethanol–water, monoglycerides–diglycerides–(65 wt% ethanol + 35 wt% water), monoglycerides–triglycerides–(65 wt% ethanol + 35 wt% water), and diglycerides–triglycerides–(65 wt% ethanol + 35 wt% water). Measurements were performed at 343.15 K using a thermostated view cell. The experimental tie‐line data for the six systems were correlated using the NRTL model for activity coefficients. Results from a simulation study using the binary interaction parameters determined for the NRTL model indicate that liquid–liquid extraction with aqueous ethanol can be used to obtain a 90 wt% monoglycerides product with up to 70% yield, in a simple process.