In this paper we introduce a lithium/sulfur–oxygen (Li/S–O2) hybrid cell that is able to operate either in an air or in an environment without air. In the cell, the cathode is a sulfur–carbon composite electrode containing appropriate amount of sulfur. In the air, the cathode first functions as an air electrode that catalyzes the reduction of oxygen into lithium peroxide (Li2O2). Upon the end of oxygen reduction, sulfur starts to discharge like a normal Li/S cell. In the absence of oxygen or air, sulfur alone serves as the active cathode material. That is, sulfur is first reduced to form a soluble polysulfide (Li2S x , x ≥4) that subsequently discharges into Li2S through a series of disproportionations and reductions. In general, the Li/S–O2 hybrid cell presents two distinct discharge voltage plateaus, i.e., one at ∼2.7V attributing to the reduction of oxygen and the other one at ∼2.3V attributing to the reduction of sulfur. Since the final discharge products of oxygen and sulfur are insoluble in the organic electrolyte, it is shown that the overall specific capacity of Li/S–O2 hybrid cell is determined by the carbon composite electrode, and that the specific capacity varies with the discharge current rate and electrode composition. In this work, we show that a composite electrode composed by weight of 70% M-30 activated carbon, 22% sulfur and 8% polytetrafluoroethylene (PTFE) has a specific capacity of 857mAhg−1 vs. M-30 activated carbon at 0.2mAcm−2 in comparison with 650mAhg−1 of the control electrode consisting of 92% M-30 and 8% PTFE. In addition, the self-discharge of the Li/S–O2 hybrid cell is expected to be substantially lower when compared with the Li/S cell since oxygen can easily oxidize the soluble polysulfide into insoluble sulfur.