The electrochemically interfacial stability between Ni foam and organic electrolyte is studied under Ar and O2 atmospheres, respectively. The potential of Ni foam cycled under Ar atmosphere does not reach 3.8V vs. Li/Li+, and is finally stabilized at ∼3.4V vs. Li/Li+. This phenomenon is the result of the electrolyte's continuous decomposition, which produces a thick layer of particles (0.8–1.2μm) covered on Ni foam surface. Ni foam under O2 atmosphere can be successfully cycled between 2.0 and 4.5V vs. Li/Li+ although there exist some precipitations on the surface, which originate from the electrolyte decomposition occurring at 4.2V vs. Li/Li+ in the initial charge. For the cycling between 2.0 and 4.0V vs. Li/Li+, Ni foam surface almost keeps intact. Our results reveal that O2 atmosphere significantly improves the electrochemical stability between Ni foam and electrolyte and thus enables Ni foam to work as current collector in rechargeable lithium-air battery.