We investigated the influence of the Sm-doped contentration on the electrical properties and PTC effect of Ba-excess BaTiO3Based Ceramics, which were fired at 1300 °C for 30 min in a reducing atmosphere and then reoxidized at 850 °C for 1 h. The results showed that the donor dopant affected PTC characteristics and the electrical properties of the BSMT ceramics, whose room temperature resistivity first decreased and then increased with an increase in the Sm3+-doped content across the range from 0.1 to 0.5 mol%. The BSMT specimens exhibited a remarkable PTC effect, with a resistance jump greater by 2.7 orders of magnitude, along with a low room temperature resistivity of 128.6 Ω∙cm at the donor-doped content of 0.3 mol%. The influence of the donor dopant on the grain size of the as-fired samples has been also investigated.