The novel submicro-spheres SiO2@LaPO4:Eu@SiO2 with core-shell-shell structures were prepared by connecting the SiO2 submicro-spheres and the rare earth ions through an organosilane HOOCC6H4N(CONH(CH2)3Si(OCH2CH3)3 (MABA-Si). The as-prepared products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and infrared spectroscopy (IR). It is found that the intermediate shell of the submicro-spheres was composed by LaPO4:Eu nanoparticles with the size of about 4, 5–7, or 15–34 nm. A possible formation mechanism for the SiO2@LaPO4:Eu@SiO2 submicro-spheres has been proposed. The dependence of the photoluminescence intensity on the size of the LaPO4:Eu nanoparticles has been investigated. The intensity ratios of electrical dipole transition 5D0 → 7F2 to magnetic dipole transition 5D0 → 7F1 of Eu3+ ions were increased with decreasing the size of LaPO4:Eu nanoparticles. According to the Judd-Ofelt (J-O) theory, when the size of LaPO4:Eu nanoparticles was about 4, 5–7 and 15–34 nm, the calculated J-O parameter Ω2 (optical transition intensity parameter) was 2.30 × 10−20, 1.80 × 10−20 and 1.20 × 10−20, respectively. The increase of Ω2 indicates that the symmetry of Eu3+ in the LaPO4 lattice was gradually reduced. The photoluminescence intensity of the SiO2@LaPO4:Eu@SiO2 submicro-spheres was unquenched in aqueous solution even after 15 days.