A carbon particle supported sulfur (C–S) composite cathode material was prepared by a chemical deposition method in an aqueous solution. The performance of the C–S cathode material with carbon particles (CP) and carbon nanofibers (CNFs) as electrical conductors and CMC+SBR as binder was evaluated in Li/S cells using cyclic voltammetry, constant current cycling, and electrochemical impedance spectroscopy. The C–S material and the electrodes were examined by scanning electron microscopy. It is found that the C–S cathode with CNFs shows improvement of not only discharge capacity but also cycling durability. It exhibits an initial discharge capacity of 1200mAhg−1, or 72% of theoretical, and retains 668mAhg−1, or 40% of the sulfur theoretical capacity after 50 cycles. The C–S electrode with CNFs has a three-dimensional network structure with regular pores, which can suppress the agglomeration of sulfur or lithium sulfide. Thus, the cell performance is improved.