Polypyrrole/vanadium oxide nanotubes (PPy/VOx-NTs) as a new high-performance cathode material for rechargeable lithium-ion batteries are synthesized by a combination of hydrothermal treatment and cationic exchange technique. The morphologies and structures of the as-prepared samples are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetry and differential scanning calorimeter (TG–DSC) and X-ray powder diffraction (XRD). The results indicate that the organic templates are mainly substituted by the conducting polymer polypyrrole without destroying the previous nanotube structure. Their electrochemical properties are evaluated via galvanostatic charge/discharge cycling, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). It is found that PPy/VOx-NTs exhibit high discharge capacity and excellent cycling performance at different current densities compared to vanadium oxide nanotubes (VOx-NTs). After 20 cycles, the reversible capacity of PPy/VOx-NTs (159.5mAhg−1) at the current density of 80mAg−1 is about four times of magnitude higher than that of VOx-NTs (37.5mAhg−1). The improved electrochemical performance could be attributed to the enhanced electronic conductivity and the improved structural flexibility resulted from the incorporation of the conducting polymer polypyrrole.