The invention discloses a hydrogen energy environment-friendly composite fuel and a preparation method thereof.The composite fuel comprises, by weight, 15-30% of a modified methanol additive and 70-85% of a hydrocarbon ether additive, the modified methanol additive comprises, by weight, 6-10% of a core agent and 90-94% of refined methanol, the modified methanol additive is also called as a fuel oil purification synergist, and the hydrocarbon ether additive is also called as a fuel oil purification synergist. The hydrocarbon ether additive comprises aromatic hydrocarbon, xylene, trimethylbenzene, alkylate oil, MTBE, naphtha, raffinate oil and C5, and the core agent comprises isopropanol, cyclohexylamine, fatty acid methyl ester, isooctyl nitrate, 2 # jet fuel, dimethyl carbonate, methyl tert-butyl ether, zinc peroxide, 2, 6-butylated hydroxytoluene, ethyl ferrocene and tetraethyl lead. According to the hydrogen energy environment-friendly composite fuel adopting the structure and the preparation method of the hydrogen energy environment-friendly composite fuel, natural combustion of methanol is changed into catalytic combustion, combustion is more sufficient, oil consumption is reduced, power is increased, and tail gas emission is obviously reduced.