In this work, two materials for secondary lithium battery cathodes formed by polyaniline–V2O5 and sulfonated polyaniline–V2O5, which have a higher charge capacity than the V2O5 xerogel, were synthesized. X-ray absorption and Fourier transform infrared spectroscopies were employed to analyze the short-range interactions in these materials. Based on these experiments, it was possible to observe significant differences in the symmetry of the VO5 units, and this was attributed to the intimate contact between V2O5 and the polymers, and to some flexibility of the VO5 square pyramids due to the low range order of the nanocomposites.