The preparation, characterization and photoreactivity of tungsten trioxide powders are presented. Tungsten trioxide powders were prepared by air annealing of various W precursors. The effects of W precursor type and pretreatment conditions on the physical properties, and photocatalytic performance of the obtained WO3 powders were examined. The photooxidation of water to oxygen and protons in the presence of reducible additives Ce4+, using the luminous and near IR illumination was used as a test reaction to evaluate the activity of the powders. Increasing annealing temperatures gave materials with a high degree of crystallinity and red-shifted the onset of light absorption. The light absorption of the obtained powders in the long wavelength region versus the type of the W precursor increased in the order: H2WO4 < (NH4)(6)W12O39 < (NH4)(10)W12O41. The level of crystallinity of the obtained powders increased in the order: (NH4)(10)W12O41 approximate to (NH4)(6)W12O39 < H2WO4. The activity of the WO3 powders depended on the type of W precursor used, annealing conditions, and the physico-chemical characteristics of the resulting powders. The activity according to the types of the W precursor increased in the order: (NH4)(10)W12O41 < (NH4)(6)W12O39 < H2WO4. The activity as a function of annealing temperature and duration of W precursors goes through a maximum at 700-800C and 4-8 h, respectively. Increasing the specific surface area of WO3 powders, did not alter the activity significantly. Addition of 0.1-1% Pt and RuO2 as co-catalysts improved the initial rates and long-term activity by about 1.3-1.5 times. Small amounts of hydrogen were also produced from photochemical reactions involving the photoexcitation of Ce3+.