Direct synthesis of vanadia onto titania-silica matrices as photocatalysts was achieved by using simple sol-gel method. This synthetic strategy, revealed that the vanadia species could be loaded into TiO2-SiO2 matrices up to 18.5 wt%. Results from FTIR indicated that at low loading amounts of vanadia species (i.e. <= 1), the formation of monolayer vanadia species onto the matrices was successfully fabricated; however, a polymeric vanadate could be formed with high loading of vanadia species. On such heterogeneous photocatalytic systems, the oxidation affinity of trichloroethylene was substantially affected by the loading amount and the degree of dispersion V2O5 particles onto the TiO2-SiO2 support matrices, indicating the exclusive effect of the V2O5 nanoparticles on this photocatalytic reaction. Clearly evident is that this polymeric vanadate was a relatively inactive photocatalysts for the oxidation of trichloroethylene. (c) 2007 Elsevier B.V. All rights reserved.