The invention relates to a preparation method of an organic/inorganic hybridization nano super-hydrophobic fiber film. The method comprises the steps of dissolving a polymer carrier in water, and heating and stirring to obtain a polymer carrier solution; mixing tetraethoxysilane, water, zinc acetate and phosphoric acid, and stirring at the room temperature to obtain a mixing solution; uniformly mixing the mixed solution and the polymer carrier solution, then performing electrostatic spinning, drying in vacuum, forging, cooling and dipping in HCl solution, and drying to obtain a SiO2 porous nano fiber film; compositing and laminating the SiO2 porous nano fiber film, pouring a liquid, and drying in vacuum to obtain the organic/inorganic hybridization nano super-hydrophobic fiber film. The super-hydrophobic nano inorganic fibers have superhigh hydrophobic performance which can be maintained under the conditions of humidity, low temperature and the like without the FAS processing, is smooth and soft in hand feeling, gets rid of the limitation of the economic cost of an organic fluorocarbon and APEO and the environment-friendly limitation, and has the advantages of low price, no pollution, wide applicable range and the like.