Two α-alumina + YSZ samples were prepared by sintering for 3 h one at 1500 °C and the other at 1700 °C. The samples were then converted to Na-β″-alumina + YSZ by vapor phase conversion. Characterization techniques such as X-ray diffraction, scanning electron microscopy, and electrochemical impedance spectroscopy in addition to dimensional geometrical changes reveal the evolution of slight anisotropy in these samples during conversion. This results in an electrical conductivity anisotropy factor of about 5.5 and 1.8 for samples sintered at 1500 °C and 1700 °C, respectively. In all samples, the higher ionic conductivity was measured across the sample thickness as opposed to parallel to the disc faces. The ionic conductivity measurements show the conductivity of about 0.15 S/cm and 0.07 S/cm at 300 °C for samples sintered at 1500 °C and 1700 °C, respectively. The larger anisotropy in samples sintered at 1500 °C is explained by the higher aspect ratio of grains in this sample and by different Na concentrations.