This study explored the superior photocatalytic performance of the nanoscale zinc oxide-yttrium oxide (ZnO - Y2O3) based composite over ZnO nanoparticles (NPs). We investigated this by following the photocatalytic degradation efficiency of methylene blue (MB). The sol-gel synthesized Y2O3 and ZnO NPs were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The spectral behaviour and photocatalytic efficiency of the proposed composite were investigated by UV-Vis spectrophotometry, steady-state and time-resolved photoluminescence (PL) measurements, respectively. The results indicated the successful formation of Y2O3 and ZnO nanoparticles with desirable structural properties. The photocatalytic degradation efficiency of the MB solution was evaluated for different concentrations of the counterparts of the ZnO - Y2O3 composite. In particular, the ZnO-5Y2O3-based composite showed superior photocatalytic activity after 150 min of UV irradiation, achieving 98.4% degradation of the MB solution compared to the 77% degradation achieved by pure ZnO. Although Y2O3 alone does not exhibit photocatalytic activity, its combination with ZnO significantly enhances the photocatalytic performance of ZnO. This improvement was attributed to the luminescence properties of Y2O3. By elucidating this unique mechanism, the performance of photocatalytic materials can be significantly enhanced. In our study, the improvement of the photodegradation rate constant (kapp) of ZnO from 0.009 min-1 to 0.0242 min-1 demonstrated the promising photocatalytic efficiency of the ZnO-5Y2O3 based composite, opening up exciting possibilities for further applications in environmental remediation and other fields.