A lithium-air battery, in which the catalytic reduction of O2 in an alkaline aqueous electrolyte and the metallic lithium in a non-aqueous electrolyte were subtly united together by a super-ionic conductor glass film (LISICON), was established in the present work. For this system, Mn3O4 based air diffusion electrode and metallic lithium were used as positive electrode and negative electrode, respectively. 500h continuous discharge performance indicates that this kind of lithium-air battery has a potential to realize continuous reduction of O2 from air to deliver energy like a fuel cell. During the long-time discharge process, the air electrode has delivered a special capacity of 50,000mAhg−1 based on total mass of catalytic electrode (carbon+binder+catalyst). This result is much higher than that of previous studies about Lithium-air batteries.