MoO2@N-doped C nanofibers (MoO2@NC NFs) were synthesized by electrospinning with polyacrylonitrile as carbon source. The in situ formed MoO2 nanocrystals are completely embedded in the carbon nanofibers, which can not only accelerate ion transition, but also act as a buffer to avoid the mechanical degradation of active material due to the volume changes during charge/discharge cycling. When used as the anode material for both Li/Na-ion batteries, the as-synthesized MoO2@NC NFs displayed excellent Li+/Na+ storage properties. As the anode for Li-ion battery, the MoO2@NC NFs display a high discharge capacity of 930 mA h g(-1) at a current density of 200 mA g(-1) for 100 cycles, and 720 mA h g(-1) at a current density of 1 A g(-1) for 600 cycles. Moreover, the discharge capacity of 350 mA h g(-1) could be realized at a current density of 100 mA g(-1) for 200 cycles for Na-ion battery.