Nanocrystalline GdPO4 : Eu3+ phosphor layers were coated on non-aggregated, monodisperse and spherical SiO2 particles by Pechini sol-gel method, resulting in the formation of core-shell structured SiO2 @ GdPO4 : Eu3+ particles. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), photoluminescence (PL), low-voltage cathodoluminescence (CL), time-resolved PL spectra and lifetimes were used to characterize the core-shell structured materials. Both XRD and FT-IR results indicate that GdPO4 layers have been successfully coated on the SiO2 particles, which can be further verified by the images of FESEM and TEM. Under UV light excitation, the SiO2 @ GdPO4 : Eu3+ phosphors show orange-red luminescence with Eu3+ 5D0-7F1 (593 nm) as the most prominent group. The PL excitation and emission spectra suggest that an energy transfer occurs from Gd3+ to Eu3+ in SiO2 @ GdPO4 : Eu3+ phosphors. The obtained core-shell phosphors have potential applications in FED and PDP devices.