A solid-state metathesis approach for the synthesis of hydrated MnV2O6 center dot xH(2)O (x = 2, 4) materials driven by mechanochemical activation energy has been demonstrated. The metathesis pathway of forming the desired product is confirmed by the presence of high lattice energy by-product such as NaCl. The structural, optical, and chemical properties of the synthesized materials are examined by powder X-ray diffraction, X-ray photoelectron spectroscopy, thermo gravimetric analysis, scanning electron microscopy, transmission electron microscopy, and diffused reflectance measurements in the UV-vis range. The valence state of Mn and V was determined to be +2 and +5, respectively, for the title compounds and the bandgap values determined showed these materials are likely to be semiconductors. (C) 2008 Elsevier B.V. All rights reserved.