Carbon nanofiber film (CNF) as anode material for lithium-ion batteries (LIBs) draws attention for its excellent cyclic stability, but its practical application is limited due to low specific capacity. Considering the advantages of pure CNF and MoS2, a flexible film which CNF covered by MoS2 (MoS2/CNF) is successfully produced and evaluated as a binder-free electrode for LIBs without mixing with carbon black and polymer binder. MoS2 nanoflakes (8.91 wt% of the composite sample) covering on CNF (MoS2/CNF-B sample) plays the key role in activating the electrochemical properties of CNF, but dense MoS2 nanoflakes (39.4 wt%) on CNF (MoS2/CNF-A) seriously limit the electrochemical properties of CNF. At 0.1 and 1.0 A g(-1), MoS2/CNF-B sample delivers 967.1 and 605.7 mA h g(-1), the capacities are almost twice as much as those of pure CNF. The initial columbic efficiency of MoS2/CNF-B sample of 76.4% is much higher than that of pure CNF sample of 62.1%. Moreover, MoS2/CNF-B sample presents no capacity decay till 100 cycles, and the cycled electrode at the 100th cycle still maintains a stable composite structure of MoS2 nanoflakes covering on CNF.