Radiative cooling technology is well known for its sub‐ambient temperature cooling performance under sunlight radiation. However, the intrinsic maximum cooling power of radiative cooling limits the performance when the objects meet the thermal shock. Here, we proposed a dual‐function strategy composed of radiative cooling and latent heat storage simultaneously enabling the efficient sub‐ambient cooling and high‐efficiency thermal‐shock resistance performance. The electrospinning and absorption‐pressing methods were employed to assemble the dual‐function cooler. The high sunlight reflectivity and high mid‐infrared emissivity of radiative film allows excellent sub‐ambient temperature of 5.1 °C. When subjected the thermal shock, the dual‐function cooler demonstrates a pinning effect of huge temperature drop of 39 °C and stable low‐temperature level by isothermal heat absorption compared with the traditional radiative cooler. The molten phase change materials provide the heat‐time transfer effect by converting thermal‐shock heat to the delayed preservation. This strategy paves a powerful way to protect the objects from thermal accumulation and high‐temperature damage, expanding the applications of radiative cooling and latent heat storage technologies.This article is protected by copyright. All rights reserved