The charge/discharge characteristics of sulfurized polyacrylonitrile composite (SPAN) cathodes with different sulfur content in conventional carbonate based electrolyte for rechargeable lithium batteries have been investigated. The good performance of SPAN in the carbonate based electrolyte indicates a material difference between SPAN and elemental sulfur/carbon composite materials. The SPAN with sulfur contents of 33.7%, 42.0% and 46.3% are prepared by control of heating time. The SPAN with sulfur content of 42.0% shows the best electrochemical performance, it can deliver stable cycling capacity over 700mAhg−1, and keep capacity retention over 97% after 80 cycles in the electrolyte of 1M LiPF6/EC+DEC. The average capacity degradation rate is less than 0.03% per cycle excluding the first discharge capacity. Prototype 100mAhLi/SPAN cell is assembled, showing energy density of 437Whkg−1 excluding the weight of package and capacity retention of 90.4% after 30 cycles at 100% depth of discharge. This study demonstrates that the sulfurized polyacrylonitrile composite in the electrolyte of 1M LiPF6/EC+DEC is a promising battery chemistry, which materials are abundant, of low cost and easily available, to fabricate Li/SPAN batteries, paving an alternative avenue to develop high performance lithium batteries for energy storage and vehicular application.