Several TiO2/SiO2 supports and supported vanadium oxide (vanadia) catalysts of varying titania and vanadia content are synthesized and characterized. Titania rutile phase is not detected for the TiO 2/SiO2 supports even up to a calcinations temperature of 1073 K. The supported vanadia catalysts were also studied for the ethane and propane ODH reaction and compared with TiO2 (Degussa P25) supported catalysts. Surface vanadia species are present on the titania or silica part of the TiO2/SiO2 support depending on the titania and vanadia loading of the catalyst. Depending on the vanadia loading in the V 2O5/TiO2/SiO2 catalyst the anatase to rutile phase transformation may occur below 1073 K. Furthermore, the ODH activity is retained or decreases less rapidly compared to the TiO2 supported catalyst as the calcination temperature is increased. Consequently, the TiO2/SiO2 supported vanadia catalysts do provide certain advantages compared to the TiO2 (Degussa P25) supported system. © 2008 Springer Science+Business Media, LLC.