Fine-grained BaTiO₃-based X7R ceramic materials were prepared and the effects of milling process on the core-shell structures and dielectric properties were investigated using scanning electron microscope, transmission electron microscope, and energy dispersive spectroscopy (EDS). As the milling time extends, the dielectric constant of the ceramics increases, whereas the temperature coefficient of capacitance at 125℃ drops quickly. The changes in dielectric properties are considered relevant to the microstructure evolution caused by the milling process. Defects on the surface of BaTiO₃ particles increase because of the effects of milling process, which will make it easier for additives to diffuse into the interior grains. As the milling time increases, the shell region gets thicker and the core region gets smaller; however, EDS results show that the chemical inhomogeneity between grain core and grain shell becomes weaker.