This invention relates to a preparation method of 4-phenylacetylene benzene anhydride. The procedures are that (1) 4-bromobenzene anhydride reacts with acetylene for 19~21 hours in spasmolytol solvent with cuprous iodide catalyst and dichlor double triphenyl phosphor and palladium, the reaction temperature is 75~850C. (2) Spasmolytol is separated and solid precipitation is mixed with acetic anhydride, the mole ratio of acetic anhydride and 4-bromobenzene anhydride is 1.5~6.0:1. Acetic acid and acetic anhydride are evaporated by heating and reflowing 30 minutes, the 4-phenylacetylene benzene anhydrite is got after recrystal of isochoric toluene and normal hexane component solvent, melting point is 151.6~152.30C, gain ratio is 90~91%.