The invention relates to a method for synthesizing a monomolecular phosphorus-nitrogen expansion flame retardant, which is characterized by: reacting pentaerythritol and phosphorus oxychloride at 80-120°C for 2-12 hours, adding the first solvent during the reaction, and the reaction ends After cooling, filtering, washing, and vacuum drying for 12-24 hours to obtain a white solid, the white solid is 1-oxo-4-hydroxymethyl-1-phospho-hetero-2,6,7-trioxabicyclo [2, 2, 2] octane (PEPA); then add the white solid (PEPA) into the second solvent, stir rapidly to dissolve it, then add isocyanate substances dropwise, and add the catalyst dropwise at the same time, stirring continuously, the reaction The time is 1 to 12 hours, the reaction temperature is 20 to 100°C, the solution changes from clear to turbid, the product is poured into ice water, an appropriate amount of inorganic acid is added dropwise, the pH value is adjusted to be acidic, a white solid is precipitated, and then washed with a washing solvent for 3 The filtered product was vacuum-dried to obtain a white or light yellow solid with a yield of 90-96%. It has the advantages of no halogen, non-toxicity, environmental protection, good application prospects and the like.