Polyaniline was electrodeposited onto reticulated vitreous carbon – RVC – in order to obtain a tridimensional composite electrode. Three variations of these electrodes were analysed: a small-anion-doped polyaniline (RVC/Pani), a polyanion-doped polyaniline (RVC/PaniPSS) and a bi-layer type formed by an inner layer of the first electrode and an outer layer of the second one (RVC/Pani/PaniPSS). These composites were characterized by cyclic voltammetry, scanning electronic microscopy and electrochemical impedance spectroscopy. Photomicrographies, voltammetric profiles and impedance data pointed to different morphological and electrochemical characteristics for polyaniline doped with small or large anions, and a mixed behavior for the bi-layer electrodes. Charge–discharge tests for these tridimensional (3D) electrodes, employed as the cathode in lithium batteries, indicated better performance for the RVC/Pani electrode. These RVC composites presented higher specific capacities when compared with those obtained for Pani deposited onto bidimensional substrates.