Complex impedance spectra of BaTiO3 with boron addition on electrical characteristics of PTCR were studied. Cole-Cole plot shows a single semicircle at room temperature (Tc) but shows a overlapping semicircle and skew circle above the Curie temperature (Tc m), which may indicate relaxational processes occurred with multiple defects, such as VBa, V0 etc, from single defect such as VBa because of thermal activation in the regions of grain boundary layer. The grain resistance, grain boundary resistance and relaxational time constant were calculated from the Cole-Cole plot and the barrier height was calculated by the Heywang model. The results show that PTC effect originates from the grain boundary. The grain resistance exhibits NTC, but the grain boundary resistance shows obviously PTC. Up to date, the Heywang model or Heywang-Jonker model is the most acceptable model to explain the PTC mechanism by phenomenal explanation.