The invention discloses a pollution/rain flashover resistant paint. The paint comprises the following components in parts by weight: 40-50 parts of silicon rubber, 40-50 parts of MQ silicon resin, 50-80 parts of a solvent, 5-20 parts of fillers, 50-70 parts of silicone acrylate resin, 0.5-3 parts of a curing agent and 3-6 parts of catalysts, wherein the silicon rubber is hydroxyl-terminated polydialkylsiloxane; the MQ silicon resin is methyl hydrogen-containing MQ silicon resin with M-Q ratio being 0.6-0.9; the solvent is one or mixture of butyl acetate, ethyl acetate and methyl acetate; the fillers are one or more of nano calcium carbonate, fumed silica, titanium dioxide and silica micropowder, which are subjected to surface modification treatment by silane; the curing agent is zirconiumisooctoate, cobalt isooctoate or cobalt naphthenate; and the catalysts are tin compounds or organic titanium compounds. The invention also discloses a preparation method of the pollution/rain flashover resistant paint.