Well-shaped Rh particles grown epitaxially on NaCl surfaces were coated with a 25 urn layer of crystalline vanadium oxide by reactive deposition in 10(-4) mbar oxygen. The Rh/VOx film was subjected to consecutive heat treatments in 1 bar oxygen and in 1 bar hydrogen up to 673 K. The structural and morphological changes were monitored by (high-resolution) transmission electron microscopy, selected area electron diffraction and electron energy-loss spectroscopy and compared to the alterations of a bare vanadium oxide film treated under equal conditions. The stoichiometry and structure of the VOx support depend on the temperature of the NaCl template and on the deposition rate. Low deposition rates and high substrate temperatures favour the generation of a pure V2O3 phase, with both V2O3 and the Rh particles in epitaxial relation to NaCl (001). A treatment in 1 bar O-2 between 300 and 573 K converts the supporting oxide into mixed V2O3, VO2 and V2O5 phases. Oxidation at 673 K induces a complete reconstruction into a single V2O5 phase, while an oxygen treatment at 723 K transforms also the Rh particles into (beta)Rh2O3. Reduction of the bare V2O5 film in I bar hydrogen yields cubic VO at 673 K, but reduction of the Rh/V2O5 film leads to VO formation already at 473 K. Finally, a reduction of vanadia-supported Rh particles at and above 573 K results in the formation of Rh/V alloy structures. (c) 2005 Published by Elsevier B.V.