We report the synthesis of beta-molybdenum carbide/carbon nanofibers (beta-Mo2C/CNFs) by electrospinning and annealing process, when exploited as an interlayer in Li-S batteries, demonstrating significantly improved electrochemical behaviors. The synthesized beta-Mo2C/CNFs with 3D network structure and high surface area are not only conducive to ion transport and electrolyte penetration but also effectively intercept the shuttle of lithium polysulfide by polar surface interaction. Moreover, the reaction kinetics of the batteries enhanced is due to the presence of beta-Mo2C, promoting the solid-state polysulfide conversion reaction in the charge-discharge process. Compared with the batteries with CNF interlayer and without interlayer, the batteries using a beta-Mo2C/CNFs interlayer with a sulfur loading of 4.2 mg cm(-2) delivered excellent electrochemical performance because of a facile redox reaction during cycling. The discharge capacity at the first cycle at 0.7 mA cm(-2) was 1360 mAh g(-1), maintaining a specific capacity of 974 mAh g(-1) after 160 cycles. Furthermore, it showed a high-rate capacity of 700 mAh g(-1) at 14 mA cm(-2). This work demonstrates the beta-Mo2C/CNFs as a promising interlayer to exploit Li-S battery commercialization.