It is particularly intriguing in the role of the solid-state dopants, which are not only responsible for the semiconductivity, but also the dielectric properties of BaTiO3 ceramics, e.g. CaO, MgO, Y2O3, CoO and MnO2 for EIA-X7R characteristics. We have chosen to investigate three important processing parameters, oxygen partial pressure (pO2) for sintering, and two alkali-earth-metal oxides, i.e. CaO and MgO for solid-state additives in order to study how microstructure and dielectric properties are determined by them. They are used in MLCC industry for the effect in attaining X7R characteristics and protecting against or improving for dc degradation. Apart from establishing the temperature-dependent dielectric properties, i.e. temperature-coefficient of capacitance (TCC), for both qualitative and quantitative analysis, crystalline phases in sintered ceramics of tetragonal mixed with cubic, orthorhombic and rhombohedral phases are studied using XRD and Raman spectroscopy. For microscopic studies, SEM and TEM techniques, e.g. CBED and LACBED, combined with EDS are used to study phases both in core-shell. We will examine and confirm the fidelity of whether core-shell grains are induced by chemical inhomogeneity, and more importantly, if the diffuse phase transition is caused by such microstructure with direct observations, as previous studies in perovskite-related ceramics, and crystalline phase determination for these grains. It is also an objective that we investigate why and how, by what mechanism, the chemically similar alkali-earth metal oxides should impart completely different (and indeed opposite) effect in protecting against dc degradation. Keywords: MLCC, dc degradation, DPT, Raman spectroscopy, electron microscopy.