Based on electrospinning technology, in this study, we fabricated poly(lactic-co-glycolic acid) (PLGA) nanofiber films with high reflectivity and scattering properties. Various films with different thicknesses and fiber diameters were fabricated by changing the electrospinning time and solution concentration, respectively. Detailed optical measurements demonstrate that the film reflectance and scattering ability increase with the thickness, whereas fiber diameter contributes little to both properties. With optimized film thickness and fiber diameter, nanofiber films feature whiteness with a reflectance of 98.8% compared to the BaSO4 white plate. Furthermore, when deposited on the reflector surface of a remote phosphor-converted light-emitting diode lamp, nanofiber films witness a correlated color temperature deviation decrease from 8880 K to 1407 K and a luminous efficiency improvement of 11.66% at 350 mA. Therefore, the nanofiber films can be applied in lighting systems as a highly reflective coating to improve their light efficacy and quality.