Coated catalysts, consisting of a compact ceramic core and a shelly coat prepared by mixing TiO2 with vanadium oxalate are investigated After thermal decomposition of the oxalate crystalline phases of vanadium oxide were observed on the anatase surface area. The thermal transformation of anatase into rutile is determined by these phases as proved by X‐ray analysis. A model describes the formation of V6O13 and the transformation of anatase into rutile by structural fits.