Li(2)S is a high-capacity cathode material for lithium metal-free rechargeable batteries. It has a theoretical capacity of 1166 mAh/g, which is nearly 1 order of magnitude higher than traditional metal oxides/phosphates cathodes. However, Li(2)S is usually considered to be electrochemically inactive due to its high electronic resistivity and low lithium-ion diffusivity. In this paper, we discover that a large potential barrier (~1 V) exists at the beginning of charging for Li(2)S. By applying a higher voltage cutoff, this barrier can be overcome and Li(2)S becomes active. Moreover, this barrier does not appear again in the following cycling. Subsequent cycling shows that the material behaves similar to common sulfur cathodes with high energy efficiency. The initial discharge capacity is greater than 800 mAh/g for even 10 μm Li(2)S particles. Moreover, after 10 cycles, the capacity is stabilized around 500-550 mAh/g with a capacity decay rate of only ~0.25% per cycle. The origin of the initial barrier is found to be the phase nucleation of polysulfides, but the amplitude of barrier is mainly due to two factors: (a) charge transfer directly between Li(2)S and electrolyte without polysulfide and (b) lithium-ion diffusion in Li(2)S. These results demonstrate a simple and scalable approach to utilizing Li(2)S as the cathode material for rechargeable lithium-ion batteries with high specific energy.