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In this investigation, CeO₂ thin films were deposited on glass substrates with different substrate temperatures by using RF Magnetron sputtering technique. The deposited films were characterized by X-ray diffraction (XRD), UV–visible spectroscopy, room temperature photoluminescence spectroscopy, micro-Raman and X-ray photoelectron spectroscopy. The thicknesses of the film were determined by using profilometer and it was varied from 0.70 μm to 0.87 μm. From the XRD results, it is evident that the film deposited at room temperature (RT) is amorphous in nature. The remarkable change in character from amorphous to crystalline is observed by increasing the substrate temperature from RT to 300 °C, and the crystallites were found to be in cubic phase with preferred orientation along (2 2 0). Calculated crystallite sizes were in the range of ∼8.6 nm. Optical characteristics were studied as a function of change in …