The invention relates to a preparation method of a solid catalyst for ozone heterogeneous oxidation, which belongs to the technical fields of environmental protection and chemical catalysts. The preparation method is to use perlite, albite, magnesium spinel, peridotite, aluminum hydroxide and lapis lazuli porous materials as carriers, and after the carrier is modified by lithium hypochlorite and bis(acetylacetonate) beryllium to expand pores, Add surfactant N-decyldimethyl-N'-trimethyl-2-hydroxypropyl ammonium dichloride to carry out surface activation treatment under ultrasonic action, then ultrasonic surface activation carrier is mixed with Composite mineralizer borax and potassium sulfate, catalyst precursor tricyclopentadiene promethium, tris(4,4,4-trifluoro-1-(2-thiophene)-1,3-butanedione) europium , Tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octenedione) dysprosium(III), holmium oxalate decahydrate rare earth organometallic compound , catalytic active center component precursor common transition metal organic compound cobalt gluconate, copper glutamate and noble metal compound gold tetrachloride potassium, terpyridine ruthenium chloride hexahydrate, in the emulsifier hexadecyl dimethyl ammonium ethyl Hydrothermal reaction is carried out under the action of sulfuric acid ester. After the reaction product is dried to remove water, it is burned in a muffle furnace at a certain temperature to obtain a solid catalyst for ozone heterogeneous oxidation.