Polyaniline–LiV3O8 (PANI–LiV3O8) nanocomposite has been chemically synthesized by an oxidative polymerization. The structure and performance of the sample have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), charge–discharge tests, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and the galvanostatic intermittent titration technique (GITT). In addition, the thermodynamics properties of as-prepared sample has also been studied. The PANI formed a network of electrically conductive paths among the LiV3O8 particles, so the active LiV3O8 material can be fully utilized for lithium extraction and insertion reactions and PANI–LiV3O8 nanocomposite exhibits much better electrochemical performance than bare LiV3O8. PANI incorporation in LiV3O8 could decrease the charge transfer resistance, increase the lithium diffusion coefficient during the lithiation process and improve the electrochemical reversibility.