In this paper, to develop PTCR(Positive Temperature Coefficient of Resistance) thermistor with high withstanding voltage, Ca were added to. the compositions of $(Ba_{0.9165-X}-Sr_{0.08}-Ca_X-Y_{0.0035})TiO_3+MnO_2$ 0.02wt%+$SiO_2$ 0.5wt%. the effects of Ca additions were researched according the increasing of Ca from 0[mol%] to 20[mol%], and the electrical properties were investigated. As increasing Ca additions from 0[mol%] to 20[mol%], the grain size of the specimens was reduced from 11.1[${mu}m$] to 6.15[${mu}m$], and also the sintered density was reduced from 5.43[$g/cm^3$] to 5.05[$g/cm^3$] and their the breakdown voltages were increased from 163[V/mm] to 232[V/mm]. It is shown that the breakdown voltage was increased with amount of Ca additions.