Background: Polystyrene nanospheres are used as a substrate for the hydrothermal coating of tungsten trioxide (WO3) to form a core-shell composite of PS@WO3. The core-shell structure is used for the next sintering step. This produces porous WO3. The focus of this study is on the role of porous WO3 in enhancing photocatalytic performance. Methods: The hydrothermal method was employed for coating, and the surface morphology, as well as the structural properties of WO3-coated PS spheres, were systematically investigated using SEM and XRD analyses. Additionally, the sintering process was introduced to enhance the material by inducing rupture in the PS sphere core, creating voids that significantly increased the material's surface area. Results: The evaluation of the effect of sintering temperature on photodegradation efficiency highlighted the crucial role of sintering temperature. Un-sintered and 300°C sintered WO3, both having a hexagonal crystalline structure, exhibited superior degradation efficiencies compared to samples sintered at higher temperatures (400°C and 500°C). In particular, the 300°C sintered WO3 outperformed its un-sintered counterpart despite identical crystalline structures. The performance of the PS@WO3 composite was assessed to determine the enhanced role of porous WO3. The porous WO3 obtained, in particular by the sintering of the core-shell PS@WO3 composites at 300°C, showed a remarkable improvement in the degradation efficiency. These composite demonstrated over 95% efficiency within 10 minutes and achieved near complete (100%) degradation for a further 10 minutes, surpassing the performance of pure WO3. It is important to clarify that while the final product was predominantly WO3 after the sintering process, the inclusion of PS served a critical purpose in creating voids during sintering. The PS@WO3 composite structure used as a resource for the preparation of porous WO3, even with a potentially reduced PS composition, has been found to play a significant role in influencing the surface area of the material, and consequently the photocatalytic performance. Conclusion: The study has highlighted the importance of crystalline structure and sintering conditions in optimizing the efficiency of photocatalytic materials. The porous WO3 obtained, in particular by the sintering of the core-shell PS@WO3 composites at 300°C, showed promising potential for applications under UV and visible LED light irradiation. These results provide valuable insights for the development of advanced photocatalytic materials with improved performance, highlighting WO3 as the key contributor to the observed improvements.