The catalytic efficiency of the materials can be boosted with the selective designing (nanostructures) including the core@shell which aids in attaining the separation of photoinduced charge carriers. However, to effectively separate the carriers and reduce the rate of recombination, tuning the thickness of the shell wall is a vital one. The one-dimensional (1D) rod-like shell wall-controlled ZnO@CeO2 core@shell structures were successfully prepared via co-precipitation and hydrothermal methods using the hexamethylenetetramine (HMTA) as a reagent. The CeO2 shell wall thickness was fine-tuned between 15 and 70 nm with a variation in the concentration of HMTA reagent. The results revealed that the concentration of HMTA played a significant role in the formation of ZnO@CeO2 core@shell structures and in tuning their thickness. The FE-SEM images evidenced the core-shell structures formation with the specific thickness and uniformity. The HR-TEM images confirmed the homogeneity and regular form of the shell thickness. The unit cell and crystallite size were identified from the XRD analysis. The constructed core-shell structures were further employed in the formula of the prototypes of sunscreen and their photoprotective performance was analyzed in the view to cut the solar light irradiation in a new sunscreen formulation. The developed core-shell ZnO@CeO2 structures showed the excellent optical absorption in both the UV as well as visible regions.