This research aims to find the best solution/material interface for improving the performance of alkaline Al-air batteries. It is found that the small addition of LiOH to a NaOH solution makes a great change in the electrochemical performance dramatically. In both 1M NaOH and 1M (90 percent NaOH + 10 percent LiOH) solutions, the corrosion behavior of aluminum and hence the Al-air battery performance were examined. The results reveal that the commercial aluminum electrode gains superior electrochemical characteristics under optimized conditions. It has a better electrochemical performance in the 1M (90 percent NaOH + 10 percent LiOH) solution. Moreover, higher anodic passivation and a lower corrosion rate than the pure 1M NaOH solution were observed. It is found that the corrosion products morphology of aluminum progresses from intergranular to uniform corrosion. The results of the scanning electron microscope (SEM) and electrochemical impedance spectroscopy (EIS) are in good agreement with electrochemical performance.