A polypyrrole-coated LiV3O8 nanocomposite was prepared as anode material (negative mass) for aqueous rechargeable lithium batteries and characterized by X-ray diffraction, scanning electron microscopy, and electrochemical measurements. Polypyrrole acts as a conducting matrix as well as a coating agent, which held LiV3O8 nanorods inside the particles during the charge/discharge cycles. Results show that the electrochemical performance of the PPy@LiV3O8 nanocomposite is significantly enhanced showing higher capacity and better rate capability as well as better cycling performance compared to pristine LiV3O8.