Inspired by the Cyphochilus scale with extreme whiteness, fluoropolymer is used as the matrix to prepare highly scattering porous polymer films through polymerization‐induced phase separation (PIPS) method. The mixture used for the PIPS technique contains a fluoride monomer, a UV photoinitiator, and porogens (cyclohexanol and perfluorooctanol). By carefully tuning the mixture parameters (cyclohexanol–perfluorooctanol and monomer–porogen weight ratios), the porous morphology can be well tailored, which induces different scattering performances. With an optimized formulation (50 wt% monomer, 25 wt% cyclohexanol, and 25 wt% perfluorooctanol), the porous film with a thickness of 55 µm can achieve an average total reflectance of ≈90%, featuring a measured transport mean free path of 1.3–1.7 µm (comparable to the 1.5 µm of the benchmark Cyphochilus scale). Further, the porous films are applied to the light‐emitting diode (LED) device and it is demonstrated that they can effectively improve the light extraction efficiency of the LED and thus enhance the luminous performance. Due to the simplicity, cost‐effectiveness, and scalability of the PIPS method, the as‐developed porous fluoropolymer films with such excellent scattering ability can find many potential applications not only in the field of optoelectronics, but also in various complex scenarios, such as daytime passive radiative cooling.