Alkali metal-oxygen (Li-O-2, Na-O-2) batteries have attracted a great deal of attention recently due to their high theoretical energy densities, comparable to gasoline, making them attractive candidates for application in electrical vehicles. However, the limited cycling life and low energy effi ciency (high charging overpotential) of these cells hinder their commercialization. The Li-O-2 battery system has been extensively studied in this regard during the past decade. Compared to the numerous reports of Li-O-2 batteries, the research on Na-O-2 batteries is still in its infancy. Although, Na-O-2 batteries show a number of attractive properties such as low charging overpotential and high round-trip energy effi ciency, their cycling life is currently limited to a few tens of cycles. Therefore, understanding the chemistry behind Na-O-2 cells is critical towards enhancing their performance and advancing their development. Chemical and electrochemical reactions of Na-O-2 batteries are reviewed and compared with those of Li-O-2 batteries in the present review, as well as recent works on the chemical composition and morphology of the discharge products in these batteries. Furthermore, the determining kinetics factors for controlling the chemical composition of the discharge products in Na-O-2 cells are discussed and the potential research directions toward improving Na-O-2 cells are proposed.