In this study, we examined efforts to increase the photovoltaic performance of GaAs single-junction solar cells using spectral conversion layers, respectively, composed of europium-doped (Eu-doped) phosphors, ytterbium/erbium-doped (Yb/Er-doped) phosphors, and a combination of Eu-doped and Yb/Er-doped phosphors. Spin-on film deposition was used to apply the conversion layers, all of which had a total phosphor concentration of 3 wt%. The chemical compositions of the phosphors were examined by energy-dispersive X-ray spectroscopy. The fluorescence emissions of the phosphors were confirmed by using photoluminescence measurements. Under laser diode excitation at 405 nm, we observed green luminescent downshift (LDS) emissions by Eu-doped phosphors at wavelengths of 479 nm to 557 nm, and under excitation at 980 nm, we observed red up-conversion (UC) emissions by Yb/Er-doped phosphors at wavelengths of 647 nm to 672 nm. The spectral conversion layers were characterized in terms of optical reflectance, external quantum efficiency, and photovoltaic current and voltage under AM 1.5 G simulations. The conversion efficiency of the cell combining Eu-doped and Yb/Er-doped phosphors (23.84%) exceeded that of the cell coated with Yb/Er-doped phosphors (23.72%), the cell coated with Eu-doped phosphors (23.19%), and the cell coated without phosphors (22.91%).