Sunscreens are crucial for skin health by protecting against the harmful effects of ultraviolet (UV) radiation. To overcome persistent limitations of irritation and discomfort in existing formulations, a high-performance radiative cooling sunscreen, CZHR, has been strategically designed. This formulation synergistically integrates cerium-doped zinc oxide (Ce-ZnO) and halloysite nanotubes (HNTs) to achieve dual UV protection and skin cooling. As a nanocarrier, HNTs effectively regulate the particle size, morphology, and oxygen vacancies of Ce-ZnO, significantly enhancing UV protection and catalytic activity. Resveratrol is further incorporated to improve UV resistance and pathogen inhibition. The resulting CZHR-based Pickering emulsion exhibits excellent UV shielding, high solar reflectance (0.73), and infrared emissivity (0.87). In vitro and in vivo tests show efficacy in alleviating UV-induced cellular damage and inhibiting biofilm formation. Notably, compared to commercial products, the CZHR sunscreen reduces skin temperature by an additional 1.7–2.9 °C. Biosafety evaluation confirms non-irritating property and negligible skin penetration. This thermal management system represents a promising platform for advanced photoprotection and radiative cooling.