The invention provides a category of perylene derivatives, that is perylene two-diimine replaced by trifluoromethyl and a preparation method thereof; wherein, the method comprises that perylene four-formate is used as the raw material to synthesize bromination perylene four-formate by brominating liquid bromine; the bromination perylene four-formate and perfluorinated iodoalkane are used as the raw materials to synthesize the perylene four-formate replaced by long chain perfluoroalkyl under the catalysis of copper powders or copper-tin alloy powder, and the bromination perylene four-formate and sodium trifluoroacetate are used as the raw materials to synthesize the perylene four-formate replaced by the trifluoromethyl under the catalysis of cuprous iodide; the long chain perfluoroalkyl or the perylene four-formate replaced by the trifluoromethyl is used as the raw material and hydrolyzed to synthesize the perylene four-formate or perylene four-formate anhydride replaced by the perfluoroalkyl under the function of inorganic alkali or chlorosulfonic acid; the perylene four-formate replaced by the trifluoroacetate and alkylamine or aniline are used as the raw material to synthesize the perylene two-diimine replaced by the trifluoromethyl .