In the present work, 2-step mechanical coating technique (2-step MCT), an advanced MCT, was proposed and carried out to form TiO2/Ti composite photocatalyst film with anatase TiO2. The microstructures and photocatalytic activity of the composite film were investigated. The results show that the proposed 2-step MCT is a simple process for forming TiO2/Ti composite film. The composite film has a microstructure with a nonuniform thickness, like random distribution islands. The TiO2/Ti composite film has high photocatalytic activity, which is related with crystallinity and volume of the TiO2 in the composite film.