Fractionation can be used to enhance the use of palm stearin-based emulsifiers (MDAG) to produce fractions rich in monoacylglycerol (MAG). The emulsifying properties of MAG with a high purity are known to be better than those of its mixture. MAG is an excellent emulsifier in bread, cakes, dairy products, mayonnaise and vegetable oil-based products. Multi-stage silica-assisted liquid-liquid extraction, which is simpler than molecular distillation, has potential as an alternative technology to replace the molecular distillation currently used for MDAG fractionation. This method integrates separation mechanisms based on solubility differences and surface adsorption. Multi-stage silica-assisted liquid-liquid extraction was systematically studied using response surface methodology (RSM). Three parameters including temperature (30°C–50°C), extraction time (15–45 min) and MDAG concentration (30%–50%) were optimised to produce a MAG-rich fraction. Optimal extraction conditions were obtained at a temperature of 39.0 ± 1.0°C, extraction time of 30.0 ± 1.0 min and MDAG concentration of 38.0 ± 1.0%. The optimum extraction parameters are closely related to the melting point and solubility of the dominant compounds in MDAG. Predicted applications in a number of appropriate food products are presented and discussed based on the fatty acid composition and thermal characteristics of each fraction.