The chemical and electrical characteristics of the grain boundary of the polycrystalline semiconducting BaTiO3 ceramics, which were synthesized by hot-press sintering Mn-coated semiconducting BaTiO3 powders, were investigated in terms of process parameters such as the amount of coating materials. Diffusion kinetic parameters of diffusing ions at particular heat-treatment conditions were obtained by fitting experimental data with computer-simulated results as well as electrical features near the grain boundary of the ceramics. Electrical features of semiconducting oxides were calculated from chemical distribution near the grain boundary; these values are similar to those obtained from impedance analysis. It indicated that this synthesis method can be used for fine control of chemical and electrical features near the grain boundary of semiconducting oxides. (c) 2004 Elsevier B.V. All rights reserved.