Sulfur is potential for primary lithium battery with high power and energy. However, the discharge capacity is limited due to the low electrochemical activity of sulfur. In this work, CuxS is incorporated into sulfur cathode synergistically to improve discharge specific capacity for primary lithium battery. For the sulfur/CuxS hybrid cathodes, discharge capacity is higher than the sulfur cathode. With the CuxS in hybrid cathodes varying from 40% to 60 wt %, the discharge capacity increases and then decreases when CuxS reaches 80 wt %. An enhanced discharge capacity of 1618.5 mAh g((s))(-1) at the current rate of 0.1C, energy density of 1107 Wh kg((CuS+S))(-1) and power density of 2827 W kg((CuS+S))(-1) are obtained when CuxS reaches 60 wt %. The good discharge performance is derived from trapping of polysusfides through chemical redox of sulfiphilic CuxS and capacity contribution of semi conductive CuxS. And, the self discharge is limited of the sulfur/CuxS hybrid cathodes. This new cooperation provides a promising approach to significantly enhance the discharge performance of primary lithium batteries.