TiO2@ZrO2@Y2O3 :Eu3+ composite particles with a core-multishell structure were synthesized through the combination of a layer-by-layer (LBL) self-assembly method and a sol-gel process. The obtained sam- ples were characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and fluorescence spectropho- tometry. The results showed that the composite particles had a core-multishell structure, spherical morphology, and a narrow size distribution. The presence of a ZrO2 layer on the TiO2 core can effec- tively prevent the reaction between the TiO2 core and a Y203 shell; the temperature for the reaction between the TiO2 core and the Y203 shell in the TiO2@ZrO2@Y2O3 :Eu core-multishell phosphor can be elevated by 300 ℃ compared to that for TiO2@ZrO2:Eu. Upon excitation of the core-multishell particles in the ultraviolet (254 nm), the Eu3+ ion in the Y2O3 :Eu3+ shell shows its characteristic red emission (611 nm, 5D0→7F2), and the photoluminescence (PL) intensity of the phosphor with the core-multishell structure was obviously greater than that of the core-shell TiO2@Y2O3 :Eu phosphor.