The high performance of lithium sulfur (Li-S) batteries is the focus of research in recent years. However, the low sulfur loading, shuttling effect in electrolyte, and poor cycling stability limit their applications. Herein, molybdenum carbide nanocrystals embedded carbon nanofibers (Mo2C@CFs: MCCFs) hybrid membrane was prepared in situ on CFs membrane based on carbonthermal reduction of ammonium molybdate. The fibrous MCCFs network is used as the current collector with Li(2)S(6)catholyte solution for Li-S batteries, which inhibits the shuttle effect and accelerates kinetics redox reaction. In addition, Mo2C, as electrocatalyst, promotes nucleation of Li2S of the MCCFs substance, which can reduce polarization and increase the specific capacity. As a result, the free-standing MCCFs@Li(2)S(6)electrode (sulfur loading: 4.74 mg) shows a capacity of 977 mAh g(-1)and maintains at 828 mAh g(-1)at 0.2 C over 250 cycles, and indicates excellent reversibility and cycling stability. Even with sulfur loading as high as 7.11 mg, the MCCF@Li(2)S(6)electrode exhibits an extremely high capacity of 5.75 mAh. Meanwhile, the Mo2C modified CFs can be effectively retarding the self-discharge behavior by trapping the polysulfides. Furthermore, the stability improvement of lithium anode state by effectively suppressing the shuttle effect of polysulfide, played an important role in enhancing the electrochemical performance.