Titanium coatings have been prepared on the surface of 1mm ZrO2 balls by mechanical ball mill, then the coatings are oxidized to photocatalyst TiO2 films at 400 similar to 600 degrees C. XRD, SEM, EDS and OM were used to analyze the microstructure of the films. The photocatalytic activity of the samples is also evaluated. After that the effects of oxidation temperature on the microstructure and photocatalytic activity of the films has been discussed. Result shows that, oxygen elements are imported into the inner coatings by the gaps existed in the Ti coatings, which makes the Ti particles oxidized from surface to core, finally the films with TiO2+Ti composite microstructure are obtained. The films have the best photocatalytic performance with degradation rate of methyl orange solution 79.08% by oxidation at 500 degrees C, this owing to the existence of anatase and the composite microstructure.