Lithium-ion batteries with graphite as the anode consume ∼10% of the active lithium from the cathode to form a solid electrolyte interphase layer during the first cycle, resulting in a reduced reversible capacity. Here, we report using Li2S as a cathode pre-lithiation material to compensate for the loss of active lithium and, consequently, enhance the specific energy of lithium-ion batteries. A Li2S material with a core-shell structure is prepared by mixing Li2S, Ketjenblack (KB) and poly(vinylpyrrolidone) (PVP) in anhydrous ethanol, and the material shows a specific charge capacity of ∼1053mAhg−1 (631mAhg−1 based on the total weight of cathode pre-lithiation materials, binders and conductive additives). The ability of this material to compensate for active lithium is investigated by coating a typical cathode LiFePO4 as an example, with the core-shell Li2S/KB/PVP via a simple and non-toxic coating method. Our results show that the LiFePO4 (Li2S)/graphite full cell exhibits a specific discharge capacity of 146.7mAhg−1 in the first cycle, which is the same as the specific discharge capacity of the LiFePO4 half cell. XPS analysis reveals Li2S decomposes into lithium ions and sulfur with release of electrons in the first charge. Such a successful extraction of the active lithium from Li2S results in excellent cycling performance with increased specific energy.