The microstructure development of the single-step, low-temperature sintered SrTiO3 GBBL capacitor materials is studied according to the microstructure analysis, mass transfer and defect chemical reactions during sintering process. The sintering mechanism is the reactive liquid phase sintering with the participation of solid state diffusion caused by the volatilization of oxygen. Insulating grain boundaries are formed by the grain boundary segregation of Li2O, which is caused by the donor enhanced volatilization of oxygen. Grains are semiconductorized during grain growth process which incorporates the donor dopant into SrTiO3 lattice.