The present invention relates to a polymer nano-composite of the functional inorganic nano-particle with intermingle prepared by electrospinning method, and the use of the composite. The precursory sol of the functional inorganic nano-particle is prepared by the sol-gel method, and is mixed with the polymer solution to form spinning fluid, adding precursor of dopant if necessary, and then the mixed spinning fluid is sprayed on to the electric collecting board with the action of the electric field force by electrospinning method to obtain functional polymer nano-composite with intermingle. The equipment of the invention is simple, the operation is easy, the components, structure and characteristics of the composite is easy to control, the structure is stable, the inorganic nano-particle is dispersed uniformly. According to the difference of the functionality of the inorganic nano-particles, the composite can be used in conducting material, antistatic material, magnetic material, electrochromic material, photocatalysis and ecology environment material, antibiosis material and biomaterial.