Perovskite oxide vanadium-doped strontium stannate (SrSn1-xVxO3) thin films with different concentrations x = 0.1–0.9 were fabricated by using pulsed-laser deposition, and the effects of V doping on the structure, optical band gap and the third-order optical nonlinearity were systematically investigated. With the increase of x value, the lattice parameters of SrSn1-xVxO3 decrease from 3.997 to 3.862 Å gradually, while the optical band gaps firstly increase from 4.18 to 4.26 eV, and then decrease to 3.66 eV with a boundary at x = 0.3. The third-order nonlinear optical responses were studied via the z-scan technique. The closed-aperture measurements show a negative nonlinear refractive index n2, and the open-aperture measurements demonstrate a saturable absorption β. Both n2 and β responses vary with the increase of V doping level. The maximum values of n2and β are 2.01×10−13 m2/W and 7.66×10−8 m/W, respectively, which are observed in the SrSn0.5V0.5O3sample. The metal-oxygen chemical bond along with the localized V5+Sn2+V5+complex contribute to the enhancement of optical nonlinearity.