An intercalated material has been prepared consisting of a regular alternation of organic/inorganic layers. The products were obtained by reacting 3,4-dihydroxyphenylalanine (DL-DOPA) with V₂O₅·nH₂O gel, which underwent an oxidative polymerization/intercalation process, forming a dark blue metallic colored film. The films were characterized using thermogravimetric analysis, UV–VIS transmission spectroscopy, FTIR, EPR, X-ray diffraction, dc conductivity, and cyclic voltammetry. The X-ray diffractograms indicate that the lamellar structure of the V₂O₅ is preserved but that the interplanar spacing increases from 1.18 to 1.38 nm. The FTIR and EPR spectra confirm that the V₂O₅ structure is preserved; however the presence of melanin-like structures induces the reduction of V^V ions to V^IV. The increase in the interplanar spacing is observed to increase the stability and reproducibility of the electrochemical insertion/deinsertion of Li⁺. This increase in stability is also observed in the electrochromic properties of the film, which are fully reproducible even after >60 oxidation–reduction cycles. The incorporation of melanin-like structures also affects the activation energy of the dc conductivity, which is reduced from 0.35 to 0.20 eV.