Conductive multilayer films have been fabricated from the alternating adsorption of the charged polymers, polypyrrole (PPy) and polyallylamine hydrochloride (PAH), on planar substrates as well as onto the surfaces of melamine formaldehyde (MF) microparticles based on the sequenced electrostatic layer-by-layer assembly technique. Hollow microcapsules are achieved after the removal of MF cores by dissolution in acid solution. The structure and conductive properties of the multilayer films and the hollow shells were characterized by UV−visible spectroscopy, phase contrast optical microscopy, atomic force microscopy, transmission electron microscopy, and scanning electron microscopy, respectively. The conductivity of all the composite films calculated from the measured resistivity is about 0.007 S/cm, which is comparable to other conductive polyelectrolyte films. The measurement of cyclic voltammetry showed that the PPy/PAH planar multilayer films, PPy/PAH-modified colloid particles, and hollow shells maintai...