Sol-gel processing routes have been developed for the production of thin films and powders in the system TeO2-TiO2 from tellurium and titanium alkoxides. The structure and properties of the resultant materials have been characterized as a function of heat treatment temperature. Pure sol-gel derived TeO2 thin films are difficult to prepare with good optical transparency due to the presence of organic impurities and/or a highly dispersed metallic tellurium phase when heated at temperatures up to approximately 340°C, with crystallization to α-TeO2 occurring when the heat treatment temperature is further increased. Additions of TiO2 were found to retard the crystallisation of the α-TeO2 but promote the formation of other TiO2 or TiTe3O8 phases. However, an optimum composition in the range 0.9TeO2 0.1TiO2 was identified, which allows optically transparent thin films to be prepared with high refractive index and offers the potential for practical device manufacture.