Uniform spherical core–shell structured SiO 2 @CaMoO 4 :Eu 3+ ,Li + phosphors were prepared by a combined homogeneous precipitation approach and combustion synthesis. CaMoO 4 :Eu 3+ ,Li + layer was grown onto submicrometer amorphous SiO 2 particles, which were synthesized by the Stöber method, via a homogeneous precipitation technique. The following combustion reaction at 600°C and simply post-annealing resulted in uniform spherical SiO 2 @CaMoO 4 :Eu 3+ ,Li + core–shell structured phosphors. The products were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectra (EDS), and photoluminescence (PL). The results show that the amorphous SiO 2 submicrospheres were coated by crystalline CaMoO 4 :Eu 3+ ,Li + nanoparticles, forming spherical core–shell structure with uniform size of ∼260nm. The powder samples showed strong red emission corresponding to 5 D 0 → 7 F 2 transitions of Eu 3+ ions under near ultraviolet (UV) or blue light. Their color coordinate (0.63, 0.36) is close to the standard of national television standards committee (NTSC) (0.67, 0.33).