Carbon-coated sulfur cathodes were prepared by sputtering method and electrochemical properties of lithium/sulfur cells were investigated. As a result of charge/discharge test, sulfur cathode having carbon layer of 180Å showed the highest capacity of 1178mAhg−1 at first discharge. Moreover, discharge capacity showed about 500mAhg−1 until 50th cycle, which is two times larger than that of no-coated sulfur cathode. This capacity increase could be considered due to the decrease of polysulfides dissolution and the enhancement of electrical contact by surface carbon layer. The changes of sulfur cathode during discharge process were investigated by SEM observation, XRD and DSC measurements. From these results, a discharge reaction mechanism of lithium/carbon-coated sulfur cell was suggested.