SrHfO3 presents high density, which makes it interesting for host lattice when it is doped with rare earths for luminescent materials. The optical and structural studies of Ce3+-doped strontium hafnate films prepared by the sol-gel process are presented in this work. Crack-free films with waveguiding performances were obtained with heat-treatments between 400°C and 700°C. The total elimination of organic compounds occurs above 800°C as indicated by Fourier transform infrared spectroscopy. The optogeometric properties (refractive index and thickness) are investigated by m-lines spectroscopy. Films structure is analysed using X-ray diffraction and transmission electron microscopy. The films crystallise from amorphous phase to pure SrHfO3 orthorhombic phase at 750°C. The HfO2 monoclinic phase superposes to SrHfO3 orthorhombic phase after heat treatment performed at 1000°C. Finally, the potentiality to prepare Ce3+ activated SrHfO3 sol-gel films with scintillation properties is explored.