The polycrystalline Ba 1-x Bi x Fe 0?9 Sn 0?1 O 3 (x50?1, 0?2, 0?3, 0?4 and 0?5) ceramics were prepared using a solid state reaction process, and the effect of Bi substitution on the microstructures and the electrical properties is investigated. The as sintered Ba 1-x Bi x Fe 0?9 Sn 0?1 O 3 ceramics showed the cubic perovskite structure with small amount of spinel BaFe 2 O 4 and some residual Fe 2 O 3 . As the Bi concentration increased, the ceramic grain size decreased and the pores or holes were reduced for the ceramics. The values of room temperature resistivity, thermistor constant and activation energy of the Ba 1-x Bi x Fe 0?9 Sn 0?1 O 3 thermistor ceramics, increasing with the rise of Bi content, were in the range of 1-1290 kV cm, 4469-7328 K and 0?385-0?632 eV respectively. The electrical properties of Ba 1-x Bi x Fe 0?9 Sn 0?1 O 3 thermistor ceramics are mainly attributed to the contribution of grains, grain shells and grain boundaries by the impedance analysis.