Hafnium titanate films are generating increasing interest because of their potential application as high-k dielectrics materials for the semiconductor industry. We have investigated sol–gel processing as an alternative route to obtain hafnium titanate thin films. Hafnia-titania films of different compositions have been synthesized using HfCl4 and TiCl4 as precursors. The HfO2–TiO2 system composition with 50 mol% of TiO2 and 50 mol% of HfO2 has allowed the formation of a hafnium titanate film after annealing at 1000°C. The films exhibited a homogeneous nanocrystalline structure and a monoclinic hafnium titanate phase that has never been obtained before in thin films. The films resulted in the formation of homogeneously distributed nanocrystals with an average size of 50 nm. Different compositions, with higher or lower hafnia contents, produced anatase crystalline films after annealing at 1000°C.