Effect of MoO3 additiion on the semiconductive BaTiO3 ceramics doped with 0.2 mole% Nb2O5 and their frequency characteristics have been investigated on the view of intergranular barrier layer model through the observation of changes in their electrical properties. The resistivity increases with the increase of MoO3 addition, but the capacitance, the frequency dependence of capacitance and the effect of positive temperature coefficient of resistivity (PTCR) decrease. It is explained by the possible increase in the thickness of potential barrier due to the formation of insulating layer and thus decrease in the degree of energy band bending. Both the PTCR effect and resistivity decrease with the increase of frequency due to the possible elimination of barrier layer at the grain boundary.