The invention discloses a composite and photocatalytic nanofiber film material containing defective Ni/NiTiO3-x/C and a preparation method thereof, and belongs to the technical field of photocatalyticmaterials. According to the material, an electrospinning technology is adopted, nickel acetate and tetrabutyl titanate are respectively taken as a nickel source and a titanium source, and the nickelacetate is dissolved in acetic acid to obtain a solution A; polyvinylpyrrolidone is added into ethyl alcohol to obtain a solution B, the solution A is added into the solution B, after uniform stirring, the tetrabutyl titanate is added, stirring continues, and a precursor solution is obtained. The electrospinning technology is adopted to prepare a composite fiber film precursor under the conditionsof specific work voltage, specific acceptance distance and specific pump pushing speed, thermal processing is conducted under protection of mixed hydrogen/argon gas, and the composite and photocatalytic nanofiber film material containing the defective Ni/NiTiO3-x/C is prepared. The material has excellent photocatalytic performance and is environmentally friendly, compared with photocatalyst powder, the porous and photocatalytic nanofiber film material of a self-supporting structure can be more easily separated from a degraded solution and has more important and actual application potential.