A facile route for the uniform growth of MoS2 nanosheets on carbon nanofibers (CNFs) via a simple hydrothermal method is reported. The CNF network provides a porous and three-dimensional scaffold for the deposition of ultrathin MoS2 nanosheets. Benefiting from the highly conductive and porous CNFs as well as the nanostructured MoS2, the coaxial MoS2@CNFnanocomposites(*), when served as a binder-free and flexible anode for Li-ion batteries, could generate a synergistic effect to gain a high electrochemical utilization of MoS2. As a result, the nanocomposites exhibit a high reversible capacity of 846mAhg−1 at 100mAg−1, excellent high-rate capability (455mAhg−1 even at 2Ag−1), and good cycling retention with only 7.4% capacity degradation after 100 cycles. The superior Li-ion storage properties enable the nanocomposites to hold great potential application in high-performance Li-ion batteries.