Tailored production of titanium dioxide thin films (TTFs) are widely used in green energy field due to their outstanding advantages. In this work, the TTFs wereSprepared by the electron beam evaporation system and annealed in air and H₂ respectively. With excellent stability, samples annealed in H₂ maintain their pale yellow in the air for nearly a year. The structure, morphology, spectral and photocatalytic properties of TTFs have been observed and discussed detailedly. Titanium oxide films annealed in H₂ have better catalytic performance than those annealed in air. The results show that Ti₃₊ can improve photocatalytic efficiency since the electronic structures of TTFs annealed in H₂ can be finely tuned by the doped Ti₃₊. The existence of a Ti₃₊ induced an electronic band below the conduction band and narrows the band gap.