Composites produced during the in situ chemical polymerization of aniline on top of a poly(ethylene terephthalate) (PET) film, in different conditions, were studied by open-circuit potential (Voc), ultraviolet-visible, and infrared spectroscopy, electrical conductivity measurements, scanning electron microscopy, and atomic force microscopy. The polymerization monitoring by Voc showed a maximum associated with the intermediate pernigraniline oxidation state and a final formation of polyaniline (PANT) in the doped emeraldine salt (ES) form. Furthermore, high electrical conductivity values mere obtained for the PANI-ES coating prepared under selected conditions. A globular formation was observed for the doped PANI-ES coating with globules of sizes of the same order and same shape of the PET, demonstrating the influence of the substrate on the coating morphology.