This contribution investigates the impact of adding transition metal of Ti to CeOy samples at various concentrations referring to 0, 15.84, 24.46, 34.46, 36.23, 38.46, 45.38% and pure TiOy, correspondingly. The samples were fabricated by the magnetron sputtering technique. X-ray diffraction (XRD) configurations demonstrate the presence of α-Ce2O3 and Ce2O3 phases with increased Ti contents in the systems. X-ray photoelectron spectroscopy (XPS) experimentation confirms the purity of the S1-sample (CeO2) and the purity of the S8-sample (TiO2). Further XPS analysis reveals that Ti incorporation in the doped systems functions as a reducing agent because of the existence of α-Ce2O3 and Ce2O3 phases. Moreover, based on UV–vis spectroscopy results, the studied samples exhibit indirect optical energy band-gaps reduced from 2.6 to 2.35 eV with the increase of Ti concentrations of 0–45.38% in (S1-S7), respectively. In reference to bandgap 2.35 eV, a slight rise in band gaps was detected for S3 sample. However, an observable increase in the band gap of 2.9 eV occurred for S8 (pure TiO2). Optical analysis of the calculated energy loss parameters demonstrates that all the studied samples reveal small amounts of energy loss. Our results suggest that the improved optical properties of Ti-doped CeOy films could serve for various optical applications.