Fiber-shaped batteries have attracted much interest in the last few years. However, a major challenge for this type of battery is their relatively low energy density. Here, we present a freestanding, flexible CNT fiber with high electrical conductivity and applied oxygen plasma-functionalization, which was successfully employed to serve as an effective cathode for Li-S batteries. The electrochemical results obtained from the conducted battery tests showed a decent rate capability and cyclic stability. The cathode delivered a capacity of 1019 mAh g−1 at 0.1 C. It accommodated a high sulfur loading of 73% and maintained 47% of the initial capacity after 300 cycles. The demonstrated performance of the fiber cathode provides new insights for the designing and fabrication of high energy density fiber-shaped batteries.