Passive radiative cooling (PRC) has emerged as a sustainable cooling technology capable of reducing surface temperatures without energy consumption by simultaneously reflecting incoming solar radiation and emitting thermal energy through the atmospheric transparency window (813 μm). Among the various materials investigated for passive daytime radiative cooling (PDRC), poly (vinylidene fluoride-cohexafluoropropylene) (PVDF-HFP) has attracted significant attention because of its high infrared emissivity, chemical stability, hydrophobicity, and ability to form hierarchical porous structures. The exceptional cooling performance of PVDF-HFP arises from its strong sunlight-scattering capability, which is primarily governed by Mie scattering from pores and embedded particles with dimensions comparable to solar wavelengths. This article reviews the fundamental mechanisms by which PVDF-HFP scatters sunlight and discusses its applications in advanced radiative cooling systems. The relationship between pore morphology, refractive index contrast, scattering efficiency, and cooling performance is analyzed, together with recent advances in composite PVDF-HFP cooling films and nanofiber membranes.