Rh nanoparticles (mean size 10 and 15 nm), prepared by epitaxial growth on NaCl surfaces, were covered with layers of crystalline vanadium oxide (mean thickness 1.5 and 25 nm) by reactive deposition in 10⁻² mbar O₂. The 1.5 nm film was further stabilized with a coating layer of 25 nm amorphous alumina. The so-obtained Rh/vanadia films, containing vanadium in the V³⁺ and V²⁺ state, were treated in 1 bar O₂ at 673 K for 1 h and thereafter reduced in 1 bar H₂ at increased temperatures, particularly between 723 and 873 K. The structural and morphological changes were followed by (high-resolution) transmission electron microscopy and selected area diffraction. Oxidation at 673 K transforms the purely vanadia-supported samples into Rh/V₂O₅, while in the alumina-supported films containing only small amounts of VO_x, the formation of topotactic V₂O₃ is observed. The formation of Rh–V alloys during the subsequent reduction is strongly determined by the intimate contact and the structural and orientational relationship between Rh particles and the surrounding VO_x phase. Reduction above 473 K transforms the support into substoichiometric vanadium oxides of composition VO and V₂O. Analysis of high-resolution images and diffraction patterns reveals the presence of different alloy phases after reduction with increasing T (from 573 up to 823 K). In the alumina-supported film (low V/Rh ratio) the epitaxial alignment between the Rh particles and the surrounding V₂O₃ phase apparently favours the primary formation of defined alloys of type V₃Rh and VRh₃, followed by VRh at higher temperature. On the contrary, mainly V₃Rh₅ is formed in the purely VO_x-supported Rh/films, due to different epitaxial relations in the initial state. Possible pathways of alloy formation are discussed.