Carbon neutrality necessitates new technologies for renewable energy utilization, active regulation of heat exchange, and material recycling to promote green and intelligent building development. Currently, the integration of these functions and characteristics into a single coating material presents a significant challenge. Here, we demonstrate a novel triboelectric and radiative cooling coating with mussel-inspired architectures, fabricated using cellulose nanofibers and Mica-TiO2 as a functional mortar and brick, respectively. The abundant polar groups and specific surface area of cellulose nanofibers enable a high accumulation of induced electrostatic charges, allowing the coating to act as a tribolayer to generate triboelectric outputs. The regularly layered arrangement of Mica-TiO2 endows fire resistance to the coating, which exhibits self-extinguishing properties and maintains 45% of its original electrical output even after direct exposure to flame for 20 s. Additionally, the created multilayered stacking morphology, as well as intense group vibrations of Mica-TiO2, facilitates high reflectivity (Rsolar = 0.9) and long-wave infrared emissivity (ϵLWIR = 0.94), achieving a daytime subambient temperature drop of 5.3 °C. Notably, the coating can be recycled easily while maintaining its triboelectric, radiative cooling, and fire-resistant properties. This work provides an innovative strategy for unifying triboelectric and radiative cooling functions, as well as recyclability, into a single coating material, offering new insights for future sustainable and energy-efficient buildings.