Jiaqi Li, Xinjian He, Yang Wu, Xinyu Li, Cunmin Wang, Xiaoyu Chen, Zhi Hong Wang, X. Wang, Heguo Li, Ming‐Peng Zhuo, Jiefeng Gao, Huan Xu
ABSTRACT Radiative cooling textiles show great promise in personal thermal management owing to zero energy consumption and favorable sustainability. While some progress has been made, challenges remain in insufficient cooling power and poor air/moisture permeability, especially in high‐temperature and humid environments. Herein, we disclose a macromolecular conformation engineering (MCE) strategy to create a multimodal poly(lactic acid) (PLA) metafabric with integrated function of high‐efficiency radiative and evaporative cooling. The strategy involves the incorporation of optically optimized MOF‐801 nanocrystals to enhance the spectroscopic properties of the electrospun PLA metafabric, which could be further enhanced by intensive stretching force to promote the molecular vibration intensity and orientation degree of PLA chains. The promoted molecular vibrations in IR region and highly ordered nano‐decorated structure together contribute to a superb sunlight reflectivity (98.6%, 0.3–2.5 µm) and selective infrared emissivity (91.7%, 8–13 µm), thus achieving an ultrahigh cooling temperature of ∼9.3°C at sunny day. Moreover, the excellent moisture adsorption capability (1.2 g/g) conferred the PLA metafabric an extra ∼3°C cooling by the evaporation mechanism. The proposed MCE strategy opens a novel avenue for efficient personal cooling in hot outdoor environments.