The microstructure and positive temperature coefficient of resistivity (PTCR) characteristics of 0.1mol%Na2Ti6O13doped 0.94BaTiO3-0.06(Bi0.5Na0.5)TiO3 (BBNT-NT001) ceramics sintered at various temperatures from 1200oC to 1350oC wereinvestigated in order to develop eco-friendly PTCR thermistors with a high Curie temperature (TC). Resulting thermistors showeda perovskite structure with a tetragonal symmetry. When sintered at 1200oC, the specimen had a uniform microstructure withsmall grains. However, abnormally grown grains started to appear at 1250oC and a homogeneous microstructure with large grainswas exhibited when the sintering temperature reached 1325oC. When the temperature exceeded 1325oC, the grain growth wasinhibited due to the numerous nucleation sites generated at the extremely high temperature. It is considered that Na2Ti6O13 isresponsible for the grain growth of the 0.94BaTiO3-0.06(Bi0.5Na0.5)TiO3 ceramics by forming a liquid phase during the sinteringat around 1300oC. The grain growth of the BBNT-NT001 ceramics was significantly correlated with a decrease of resistivity.All the specimens were observed to have PTCR characteristics except for the sample sintered at 1200oC. The BBNT-NT001ceramics had significantly decreased ñrt and increased resistivity jump with increasing sintering temperature at from 1200oC to1325oC. Especially, the BBNT-NT001 ceramics sintered at 1325oC exhibited superior PTCR characteristics of low resistivityat room temperature (122Ω·cm), high resistivity jump (1.28×104), high resistivity temperature factor (20.4%/oC), and a highTc of 157.9oC.