Grain boundary chemistry and electrical characteristics of polycrystalline BaTiO3 ceramics, which were prepared with sol-gel surface-coated semiconducting powders, were investigated. Mn ions were coated on the powder surface by sol-gel coating-techniques. The additives coated on the surface of the powders were observed to be present near the grain boundaries of the ceramics. The ceramics exhibit the PTCR characteristics with a resistivity jump ratio(Pmax/Pmin) of about 2$ imes$103. With raising the temperature from room temprature to 20$0^{circ}C$, the oxidation state of the Mn ions varied from Mn3+ to Mn2+ in the coating layers. Near the grain boundaries an excessive negative charge layer of about 20nm was formed.