This work was aimed to produce high tetragonal, pure, and spherical BaTiO3 nanopowder through combined wet-chemical and rapid calcination process. Lattice parameters, crystal structure, and bonding characteristics of BaTiO3 nanopowder were determined from Rietveld refinement and maximum entropy method. The statistical Weibull distribution analysis described the formation of narrow size particle distribution. Selective sintering additive and optimum temperature profile successfully consolidated the nanoparticles without substantial grain growth. The grain exhibited a typical ferroelectric core domain, whereas, the grain shell apparently composed of nonferroelectric phase. The process described here can be implemented to the preparation of other nanoparticles for commercialization that is suitable to be obtained via this approach.