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Passive daytime radiation cooling (PDRC) has gained considerable attention as an emerging and promising cooling technology. Polymer‐based porous materials are one of the important candidates for PDRC application due to their easy processing, free of inorganic particle doping, and multifunctionality. However, the mechanical properties of these porous materials, which are critical in outdoor services, have been overlooked in previous studies. Herein, a nonsolvent‐induced phase separation (NIPS) method combined with ambient pressure drying to prepare polyethylene‐polysilicate all‐polymer porous coatings is developed. The coatings possess a Cyphochilus beetle‐like skeleton structure with optimal skeleton size, laminated anisotropy, and high volume fraction (64 ± 1%). These structure features ensure a maximum skeleton density without optical crowding, thus enhancing light scattering and stress dispersion, and balancing optical and mechanical properties. The coatings exhibit significant mechanical robustness (only ≈70 µm thickness reduction after 1000 Taber abrasion cycles at a 750 g load without influencing optical performance), durability, optical properties (a solar reflectance of ≈95% and an average near‐normal thermal emittance of ≈96%), and PDRC performance (realizing sub‐ambient cooling of ≈3–6 °C at midday with different weather conditions). The work provides a new solution to improve the practicability of polymer‐based porous coatings in PDRC outdoor services and other fields. [ABSTRACT FROM AUTHOR]