The invention provides a preparation method of a super-hydrophobic fibrous membrane, and belongs to the field of high polymer materials. The method comprises the steps that a hydrophobic organic high polymer material and polymeric microspheres are mixed in a solvent, stretching slenderization is performed through an electrostatic spinning method to form fiber, and finally the super-hydrophobic fibrous membrane of the micro-nano structure composed of fiber and microspheres is obtained. The fiber diameter of the prepared super-hydrophobic fibrous membrane is 1-5 micrometers, and the size of the microspheres is 800 nanometers to 3 micrometers. The preparation method is simple and easy to implement and good in repeatability. The polymeric microspheres in the super-hydrophobic fibrous membrane are embedded in the fiber, the super-hydrophobic fibrous membrane has the excellent super-hydrophobicity and reutilization rate, can effectively block particulate pollutant in air, can be adopted as a base material for preparing an anti-haze mask, and has the huge potential application value.