Photoelectron-hole separation efficiency plays an important role in the enhancement of the photocatalytic activity of photocatalysts towards the degradation of organic molecules. In this study, TiO2/TiOF2 heterostructured composite powders with suitable band structures, which structures are able to separate photoelectron-hole pairs, have been synthesized using a simple and versatile ultrasonic spray pyrolysis process. In addition, their phase volume fractions have been controlled by varying the pyrolysis temperature from 400 oC to 800 oC. The structural and optical properties of the synthesized powders have been characterized by X-ray diffraction, scanning electronic microscopy and UV-vis spectroscopy. The powder with a phase volume ratio close to 1, compared with single TiOF2 and other composite powders with different phase volume fractions, was found to have superior photocatalytic activity for the degradation of rhodamine B. This result shows that the TiO2/TiOF2 heterostructure promotes the separation of the photoinduced electrons and holes and that this powder can be applicable to environmental cleaning applications.