Self-standing membranes of porous carbon nanofiber (PCNF)@MoS2 core/sheath fibers have been facilely obtained through a combination of electrospinning, high-temperature carbonization and the solvothermal reaction. PCNF fibers with porous channels are used as building blocks for the construction of hierarchical PCNF@MoS2 composites where thin MoS2 nanosheets are uniformly distributed on the PCNF surface. Thus, a three-dimensional open structure is formed, which provides a highly conductive pathway for rapid charge-transfer reactions, as well as greatly improving the surface active sites of MoS2 for fast lithiation/delithiation of Li+ ions. The highly flexible PCNF@MoS2 composite membrane electrode exhibits synergistically improved electrochemical performance with a high specific capacity of 954 mA h g(-1) upon the initial discharge, a high rate capability of 475 mA h g(-1) even at a high current density of 1 A g(-1), and good cycling stability with almost 100% retention after 50 cycles, indicating its potential application as a binder-free anode for high-performance lithium-ion batteries.