Vanadium oxide/polyaniline nanotubes were produced by cationic exchange between hexadecylamine and polyaniline after the synthesis of vanadium oxide nanotubes by sol–gel method followed by hydrothermal treatment. The local structure of this hybrid material was studied by high-resolution transmission electron microscopy, infrared and Raman spectroscopy and small angle X-ray diffraction technique. The results show that polyaniline is intercalated in the interlamellar space of the vanadium oxide nanotube forming a hybrid material with defined morphology. Electrochemical impedance spectroscopy experiments have shown that the apparent diffusion coefficient for nanotubes with template was approximately 1×10−9 cm2 s−1. Nanotubes with polyaniline presented an apparent diffusion coefficient at least one order in magnitude higher than the parent material “with template”, comparable with other vanadium oxide described in the literature, revealing a promising material for utilization as cathode for ion-Li batteries.