A novel solar-driven TiO₂ nanofilm (V_O–N–TiO₂ (A/R) nanofilm), which was obtained by self-structure modifications, was designed on a Ti substrate surface. The V_O–N–TiO₂ (A/R) nanofilm showed a three-dimensional pine branched-like structure and a disordered lattice structure, which consisted of V_O, N-doping and an anatase/rutile phase, was built in the V_O–N–TiO₂ (A/R) nanofilm. The experimental results show that the band gap of the V_O–N–TiO₂ (A/R) nanofilm can be narrowed to 0.72 eV and 2.4 eV and that it exhibited excellent optical absorption capacity in the 200–2500 nm region. Using the V_O–N–TiO₂ (A/R) nanofilm to degrade methyl orange, the removal efficiency could reach 96% within 150 min under sunlight, which shows its high photoelectrocatalytic activity and stability.