In order to examine the effect of CuO and Al2O3 addition on the electrical conductivity of ZnO, both Al2O3 (0, 1, 2, 5, 10at.%) and CuO (1, 5at.%) were added to ZnO. Al2O3 addition (~2at.% Al) increased the total electrical conductivity of ZnO which was already decreased by CuO doping effect Above solid solubility of Al (~2at.%), ZnAl2O4 formed and the total electrical conductivity decreased due to the decrease of sintered density. Impedance measurements were used to know the reason and degree of contribution of three resistive elements, ZnO grain, ZnO/CuO, and ZnO/ZnO grain boundaries, to the total electrical conductivity changed.