The temperature dependence of ionic conductivity in a Li-stabilized β′′-alumina ceramics has been investigated using complex impedance analysis to explore the behavior patterns of its bulk and grain boundary conductivities between 200° and 800°C. The bulk and grain boundary ionic conductivities with activation energies of 0.14eV and 0.25eV, respectively, were obtained for the material coated with Au sputtered films as electrodes in the temperature range 300° to 600°C. The grain boundary conduction behavior changed from multi-relaxation to single-relaxation with increasing temperature. It has been found that the complex impedance plots of the materials are considerably influenced by electrode materials used and their morphology. This naturally leads to wrong conclusions on the conduction behaviors of the materials. A material with Pt sputtered film electrodes had bulk and grain boundary conductivities about half as low as those for the same material with Au electrodes.