To explore thermal stability of TiO2-ZrO2 support, and dispersion and temperature stability of MoO3/TiO2-ZrO2 catalyst these systems were subjected to thermal treatments from 773 to 1073 K and were examined by X-ray photoelectron spectroscopy, X-ray diffraction, and FT-infrared techniques. The TiO2-ZrO2 mixed oxide support was obtained by a homogeneous coprecipitation method and MoO3 (12 wt.%) was impregnated over the 773 K calcined support by adopting a wet impregnation procedure. Characterization results suggest that the TiO2-ZrO2 when calcined at 773K is in X-ray amorphous state and gets converted into a crystalline ZrTiO4 compound beyond 873 K. The ZrTiO4 compound is thermally quite stable up to 1073 K calcination temperature in the absence of molybdena on its surface. In the case of MoO3/TiO2-ZrO2 catalyst, the molybdenum oxide is in highly dispersed state on the support surface when calcined at 773 K. However, above 773 K calcination it selectively interacts with ZrO2 portion of the TiO2-ZrO2 binary oxide and readily forms ZrMo2O8 compound by liberating TiO2. The ZrMo2O8 compound formation proceeds in a two-step process. In the first step, there is an incorporation of Mo6+ ions into the ZrO2 oxide matrix and then the crystal growth occurs. The liberated TiO2 appears in the form of both anatase and rutile phases with varying intensities.