The invention relates to a preparation method of an ozone heterogeneous oxidation solid catalyst, and belongs to the technical field of environmentally-friendly and chemical catalysts. The preparation method comprises the following steps: by taking gamma-aluminum oxide, barite, perlite, albite, aluminum hydroxide and phosphorite as carriers, reaming the carriers with lithium hypochlorite and bis(acetylacetone) beryllium, then adding bidecalkyl dimethyl ammonia chloride serving as a surfactant for activation treatment under ultrasonic action, putting the carriers into a hydrothermal reaction kettle for hydrothermal reaction together with borax and potassium sulfate which serve as composite mineralizers, tetra(2,2,6,6-tetramethyl-3,5-hepta-diketo acid) cerium (IV), tri(3-trifluoroacetyl-D-camphor) praseodymium (III), terbium acetate hydrate and thulium trifluoromethane sulfonate (III) which serve as catalytic active auxiliary precursors and lysine manganese, cupric glutamate, zirconium ammonium carbonate and terpyridyl ruthenium chloride hexahydrate which serve as catalytic active center precursors under the action of dimethyl bioctadecalkyl ammonia chloride serving as an emulsifier, drying a reaction product to remove water, and firing the reaction product in a muffle furnace, thus obtaining the ozone heterogeneous oxidation solid catalyst.