The aim of this work is to assess the evolution of the structural and optical properties of BixTiyOz films grown by rf magnetron sputtering upon post-deposition annealing treatments in order to obtain good quality films with large grain size, low defect density and high refractive index similar to that of single crystals. Films with thickness in the range of 220-250 nm have been successfully grown. After annealing treatment at 600 °C the films show excellent transparency and full crystallization. It is shown that to achieve larger crystallite sizes, up to 17 nm, it is better to carry the annealing under dry air than under oxygen atmosphere, probably because the nucleation rate is reduced. The refractive index of the films is similar under both atmospheres and it is very high (n =2.5 at 589 nm). However it is still slightly lower than that of the single crystal value due to the polycrystalline morphology of the thin films.