As a sulfur-containing cathode material, sulfide polyacrylonitrile (SPAN) is expected to be used for long-life lithium–sulfur battery because there is no shuttle effect occurred in its charge process. However, its specific capacity and discharge potential need to be further improved to satisfy the urgent demands for high-performance batteries. In this paper, Te0.045S0.955PAN composite was synthesized by co-heating Te x S1- x and PAN, and the superior electrochemical performance to that of SPAN was obtained because of doping Te with high conductivity. The as-prepared Te0.045S0.955PAN composite possessed the specific capacity of 675 mAh g−1 after 100 cycles at the current density of 0.1 A g−1 with high capacity retention of 96.6% compared to the second cycle. Especially, during cycling, Te0.045S0.955PAN showed average discharge voltages of 1.88–1.91 V, which were higher than 1.85–1.88 V for SPAN at the same current density. Thus doping Te provides a new strategy for increasing the energy density of SPAN.