Non-stoichiometric substituted cerium vanadates, MxCe1-xVO4 (M = Li, Ca and Fe), were synthesized by solid-state reactions. The crystal structure was analyzed by powder X-ray diffraction and it exhibits a tetragonal zircon structure, crystallizing in the space group I41/amd with a = 7.3733(4) and c = 6.4909(4) Å and Z = 4. Particle sizes were in the range of 600-800 nm, as observed by scanning electron microscopy. The thermal analysis of the compounds showed phase stability up to 1100 °C. The UV diffuse reflectance spectra indicated that the compounds have band gaps in the range of 2.6-2.9 eV. The photocatalytic activity of these compounds was investigated for the first time for the degradation of different dyes, and organics, the oxidation of cyclohexane and the hydroxylation of benzene. The degradation of dyes was modeled using the Langmuir-Hinshelwood kinetics, while the oxidation of cyclohexane and hydroxylation of benzene were modeled using a free radical mechanism and a series reaction mechanism, respectively. © 2009 Elsevier B.V. All rights reserved.