The modified polymer-network gel route has been developed to prepare a multilayer core-shell structure of BaTiO3-based dielectric ceramics. The core of particle was BaTiO3, whereas 0.7BaTiO(3)-0.3Bi(Zn1/2Ti1/2)O-3 (0.7BT-0.3BZT) and Nb oxides were coated as the multilayer shell compositions, which were confirmed by energy dispersive spectroscopy testing. The dielectric properties of BaTiO3-based samples with multilayer core-shell structure were found to meet the X9R specification. The dielectric constant was 1190 and the dielectric loss was 1.3% at room temperature.