Radiative cooling can alleviate urban heat island effects and passively improve personal thermal comfort. Among many emerging approaches, infrared (IR) transparent films and fabrics are promising because they can allow objects to directly radiate heat through bands of atmospheric transparency while blocking solar heating. However, achieving high solar reflectance while maintaining IR transmittance using scalable nanostructured materials requires control over the shape and size distribution of the nanoscale building blocks. Here, we investigate the scattering and transmission properties of electrospun polyacrylonitrile (PAN) nanofibers that feature spherical, ellipsoidal, and cylindrical morphologies. We find that nanofibers that have ellipsoidal beads exhibit the most efficient solar scattering, mainly due to the additive dielectric resonances of the ellipsoidal and cylindrical geometries, as confirmed through electromagnetic simulations. This favorable scattering decreases the amount of material needed to reach above 95% solar reflectance, which, in turn, enables high infrared transmittance (>70%) despite PAN’s intrinsic IR absorption. We further show that these PAN nanofibers (nanoPAN) can enable cooling of surfaces with relatively low solar reflectance, which is demonstrated by covering a reference blackbody surface with beaded nanoPAN. During peak solar hours, this configuration lowers the temperature of the black surface by approximately 50 °C and is able to achieve as low as 3 °C below the ambient air temperature. More broadly, our demonstration using PAN, which is not as IR transparent as more commonly used polyethylene, provides a method for utilizing lower purity materials in radiative cooling.