The invention provides a synthesis method of monoglyceride containing a phase transfer agent. The synthesis method comprises the following technological steps: adding 25 to 40 weight percent of natural oil, 54 to 73 weight percent of glycerol and 1 to 3 weight percent of the phase transfer agent into a 500mL three-mouth flask; stirring for 10 to 30min to sufficiently mix the natural oil, the glycerol and the phase transfer agent; pre-heating to 50 to 80 DEG C; dropwise adding 1 to 3 weight percent of an alkaline catalyst; heating to 180 to 200 DEG C and stirring and reacting for 2 to 6h; afterreaction is finished, adding an acid solution and neutralizing the pH (Potential of Hydrogen) of a reaction system to 6 to 7; rapidly cooling to 70 to 80 DEG C to obtain a monoglyceride crude product; S4: washing with water and filtering to obtain a white solid; finally, separating and purifying through molecular distillation to obtain the high-purity monoglyceride. The synthesis method providedby the invention has the beneficial effects that the miscibility of the oil and the glycerol is increased, the reaction is promoted, the conversion rate of the monoglyceride is high and the purity ofa product is high.