This study introduces a new flexible cathode that contains no binder, conductive additive and current collector, but instead consists solely of a sulfurized polyacrylonitrile nanofiber (SPAN) web which is prepared by a simple pyrolysis process with low cost raw materials. This not only exhibits good electrochemical properties, but also a high flexibility, rollability, and bendability to 180° without fracture. Its feasibility as a cathode for a low cost and flexible Na/S battery is subsequently evaluated on the basis that S, PAN, and Na are cheap materials. The SPAN web delivers a high first discharge capacity of 604 mAh g−1 – electrode (1473 mAh g−1 – sulfur) at 0.01 C based on sulfur content. In cycle performance at 0.1 C, a first discharge capacity of 342 mAh g−1 – electrode is obtained and remains over 266 mAh g−1 – electrode after 200 cycles along with the coulombic efficiency near 100% from the second cycle. In terms of rate capability, it is shown to be capable of delivering a capacity of as high as 71 mAh g−1 at 1 C. The reversible electrochemical reaction of the SPAN web with Na is related to a reversible bond between the C–S and S–S bonds of the SPAN web.