The invention relates to a preparation method of polyphosphoester. According to the method, phosphorus oxychloride, dialkyl phenol and hydroquinone are prepared into polyphosphoester through a one-step method, and finally the polyphosphoester is terminated by using phenol. The method includes the steps that the phosphorus oxychloride and the dialkyl phenol are used for generating monomer monophenyl ester, then polymerization is conducted through the hydroquinone to obtain a poly-phospholipid intermediate, and the intermediate is terminated by using phenol. The polymerization degree is 1-20. The method is carried out at normal pressure according to synthesis conditions, the process is simple, the safety coefficient is high, and the polyphosphoester is wide in application range, can serve asa solid flame retardant, has the advantages of being resistant to volatilization, migration and radiation, high in heat resistance, good in compatibility, low in toxicity and durable in flame retardant effect, can serve as a plasticizer for materials, and has the advantages of being high in toughness, small in brittleness and capable of improving the mechanical properties such as material notch impact strength.