The standard emeraldine base (EB) form of polyaniline and the product obtained by the oxidative polymerization of aniline using a pH-stat method at a constant pH of 2.5 are investigated. The morphology of the pH-stat product was examined using scanning electron microscopy and transmission electron microscopy. The prevalence of self-assembled nanotubes in the pH-stat product is confirmed. The structural differences between the EB and pH-stat products are revealed by FTIR and solid-state NMR experiments. On the basis of these investigations, the presence and the role of the oligomeric material in the formation of nanotubes is confirmed.