LiV3O8–polyaniline nanocomposites have been synthesized via chemical oxidative polymerization directed by the anionic surfactant sodium dodecyl benzene sulfate. The polyaniline particles are uniformly coated on the LiV3O8 nanorods. The composite with 12 wt.% polyaniline retains a discharge capacity of 204 mAh g−1 after 100 cycles and had better rate capability (175 mAh g−1 at 2 C and 145 mAh g−1 at 4 C) than the bare LiV3O8 electrode in the potential range of 1.5–4.0 V. The polyaniline coating can buffer the dissolution into the LiPF6 electrode that occurs in LiV3O8 during cycling. The charge transfer resistance of the composite electrode was much lower than that of the bare LiV3O8 electrode, indicating that polyaniline coating significantly increases the electrical conductivity between the LiV3O8 nanorods. Polyaniline is a conductive binder which buffers the dissolution of LiV3O8 into the electrolyte and reduces the contact resistance among nanorods, so performance of the composite is significantly improved.