Here we present the synthesis of the efficient nanophosphor Sr2Si5N8:Eu2+ (D50 = 144 nm) by a simple milling approach, its strong Rayleigh scattering, and its film applications to white LED and silicon solar cell as a downshifting medium. The final nanophosphor product showed the quantum efficiency comparable to the bulk phosphor which is, to our knowledge, the highest record of nitride nanophosphors. Especially the nanophosphor showed the more tail emission at the shorter-wavelength side of the emission spectrum and the faster thermal quenching with the more spectral broadening along with the temperature due to Rayleigh scattering. Also the lowering in the excitation spectrum was observed due to lower absorbance. Finally, the nanophosphor-dispersed polyvinyl alcohol (PVA) film was made, and its applications to white LED and silicon solar cell as a downshifting medium demonstrated that it gave the high color rendering property in white LED in spite of still lower luminous efficiency, and it caused the increase in efficiency of silicon solar cell.