The invention discloses a nano-TiO2-polyimide hybrid thin film having an excellent atomic oxygen resisting property. The ano-TiO2-polyimide hybrid thin film having the excellent atomic oxygen resisting property is characterized in that: firstly, vinyl trichlorosilane is subjected to hydrolytic condensation to obtain octavinyl polyhedral oligomeric silse-squioxane; the vinyl of the octavinyl polyhedral oligomeric silse-squioxane and the allyl of allyl glycidyl ether are subjected to a catalytic polymerization reaction to obtain epoxy polyhedral silse-squioxane; the epoxy polyhedral silse-squioxane is hydrolyzed through tetrabutyl titanate, is annealed at the high temperature and is reduced to obtain nano-TiO2, finally the nano-TiO2 is filled, and the epoxy polyhedral silse-squioxane is hybridized and crosslinked, and is subjected to film casting and temperature programming imidization to obtain the nano-TiO2-polyimide hybrid thin film having the excellent atomic oxygen resisting property. The hybrid thin film is prepared by hybridizing and crosslinking the epoxy polyhedral silse-squioxane, a layer of dense SiO2 is produced on the surface of the material when the hybrid thin film is under the condition of high temperature or is eroded by the atomic oxygen, then the erosion of the material by the oxygen atom is prevented, and the hybrid thin film has the excellent atomic oxygen resisting property.