A flexible carbon nanofiber membrane (NFM) containing uniformly dispersed MoO2 nanoparticles is facilely fabricated via electrospinning and subsequent controlled reduction-carbonization. This NFM is used directly as a binder-free anode in lithium-ion batteries (Ins). The self-standing carbon/MoO2 (C/MoO2) NFM electrode has a good capacity retention, a satisfactory rate capability and a high reversible capacity of 811 mAh g(-1) after 100 cycles at a current density of 100 mA g(-1), which is superior to most other MoO2-based anodes. The superior electrochemical properties of the resultant C/MoO2 NFM are attributed to the cooperative effects from the excellent conductivity of the carbon nanofiber matrix, the high electrochemical performance of MoO2, the unique one-dimensional nanofiber structure and the three-dimensional porous network structure. The present C/MoO2 NFM may be an attractive candidate as an anode material for LIBs.