The invention relates to a preparation method of an ozone heterogeneous oxidation solid catalyst and belongs to the technical field of environmental-friendly and chemical engineering catalysts. The preparation method comprises the following steps: by taking erionite, garnet, medical stones, wollastonite, coal ash and gangue as a carrier, after chambering and modifying the carrier through lithium hypochlorite and di(acetylacetone) beryllium, adding a surfactant dodecyl trimethyl ammonium chloride for surface activating treatment under the action of ultrasonic waves; then performing a reaction on the ultrasonic surface activated carrier in a hydrothermal reaction kettle and a compound mineralizer borax and potassium sulfate and catalytic active auxiliary agent precursors isoproscandium oxide (III), a tri(hexafluoroacetyl acetone) yttrium (III) dihydrate, tetra(2,2,6,6-tetramethyl-3,5-heptanedionato) cerium (IV) and thulium trifluoromethanesulfonate (III); and performing a hydrothermal reaction with catalytic active central compound precursors a titanocene ring substituted salicylic acid complex, vanadium isonicotinoyl hydrazone pyruvate, nickel citrate and potassium dithiocyanoargentate (I) under the action of an emulsifier dimyristyl dimethyl ammonium chloride, drying a reaction product to remove water, and firing the reaction product in a muffle furnace to obtain the ozone heterogeneous oxidation solid catalyst.