A novel process was developed in order to solve the problems in the manufacturing of p-nitrophenyl acetate (PNPA) , such as equipment corrosion and low yielding. The p-nitrophenyl acetate was synthesized by the acetylization of sodium p-nitrophenolate, which was prepared by the hydroxylation of pnitrochlorobenzene (PNCB) under pressure. The effects of reaction temperature, reaction time, alkali liquor concentration on the synthesis were studied. The proper technological conditions of sodium p-nitrophenolate preparation were given as follows:  140 ℃,  0.3 MPa, the reaction time is 10 h, the molar ratio of sodium hydroxide and p-nitrochlorobenzene was 2.5, the optimal mass fraction of lye was 15%. The yield of p-nitrophenyl acetate was 90.6%.