To obtain easily recycled photocatalyst and improve the reusing practicability for waste water treatment, Bi2O3 films were prepared by a plasma spray-chemical vapor deposition method , and the effects of deposition temperature and heat-treatment temperature on the morphology and phase composition of Bi2O3 films were investigated. The morphology and composition of the films were characterized by field-emission scanning electron microscopy, X-ray diffraction and high-resolution transmission electron microscopy. The band gaps of α/β-Bi2O3 at different heat treatment temperatures were determined by ultraviolet-visable diffuse reflectance spectrometry. The results show that the deposition temperature and heat-treatment temperature affect the microstructure of Bi2O3 films and the proportion of α and β phases, while the influence of deposition temperature is more dominant rather than that of heat-treatment temperature. The proportion of β phase gradually converts to α phase and the band gap of α-Bi2O3 and β-Bi2O3 increases when the heat-treatment temperature increases. The Bi2O3 films exhibit a good photocatalytic degradation performance for Methyl Orange and Bisphenol A.