In order to investigate the influences of ion implantation and vacuum annealing on the structure and properties of titanium oxide (TiO2) film, rutile titanium oxide film was synthesized on Si wafer using the unbalance reactive magnetron sputtering method, and then modified by phosphorus ion implantation and succeeding vacuum annealing. The experimental results show that an increase in implantation dose and energy will aggravate the damage to the crystalline structure of the film. After vacuum annealing, a broadening and red shift occurred to Raman peaks for both the implanted and unimplanted titanium oxide films, and the sheet resistance of the film decreased to 100—200 Ω/cm2, because of the energy band structure change caused by oxygen defects and low-valent titanium.