Personal daytime radiative cooling (PDRC) materials have high sunlight reflection and high selective emis-sivity to outer space in the main atmospheric window, demonstrating huge potential in energy-saving for sustainable development. Recently, polymer-based membranes for radiative cooling have been widely re-ported, due to their easy processing, low cost, and unique optical performance. However, the desired high sunlight reflectance of PDRC materials is easily dampened by environmental aging, high temperature, and ultraviolet (UV) irradiation, resulting in reduced cooling performance for most polymers, adverse to large-scale practical applications. In this work, we demonstrate a novel polyimide nanofiber (PINF) membrane with a fluorine-containing structure via typical electrospinning technology. The resultant PINF membrane exhibits high sunlight reflectance, UV resistance, and excellent thermal stability, rendering anti-aging day-time radiative cooling. The sunlight reflectance of PINF membranes could maintain constant in the aging test for continuous 720 h under outdoor solar irradiation, exhibiting durable and long-term personal day-time radiative cooling performance.(c) 2023 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science & Technology.