A composite, LiV3O8 -polypyrrole (PPy), was synthesized by a low-temperature solution route followed by an in situ polymerization method. The as-prepared powders consisted of nanosized PPy distributed homogeneously within the layered lithium trivanadate. The electrochemical properties of LiV3O8–PPy composite were systematically investigated and compared with bare lithium trivanadate. It was found that the electrochemical performance of the LiV3O8–PPy composite was significantly enhanced, with a specific capacity of ∼183mAhg−1 retained after 100cycles . This suggests that nanostructured PPy could work well as a polymer-conducting matrix and also as a binding material to improve the overall electrochemical properties of the LiV3O8 when used as a cathode material in lithium-ion batteries.