The invention discloses a methanol diesel fuel complex additive and a preparation method thereof. The complex additive is prepared from the following raw materials in parts by volume: 1-4 parts of diethyl phthalate, 1-8 parts of n-butylamine, 1-9 parts of isooctanol, 1-6 parts of cyclohexanone, 13-42 parts of lauryl methacrylate, 7-30 parts of mixed fatty glyceride, 1-5 parts of phenyl propargyl ether, 1-8 parts of dihexadecyl dimethyl ammonium chloride, 2-12 parts of ethyl formate, 2-14 parts of isooctyl nitrate and 1-6 parts of polyoxyethylene hexadeeylalkyl ether selies. The methanol diesel fuel complex additive can enable methanol diesel fuel to be evenly mixed and to be stably stored for more than 6 months, which effectively improves the fire behaviour of the methanol diesel fuel and inhibits the volatilization when the methanol content is higher; moreover, the production process is simple and the use is convenient, thereby being beneficial to the popularization and application of the methanol diesel fuel.