Nanostructures of polyaniline (PANI) and PANI with embedded carbon nanotubes (CNT) were synthesized through a chemical method of self-organization. An oxidative polymerization process was performed in the monomer acid solution with the presence of a surfactant and the addition of multi-walled CNT. The CNT were added with and without pretreatment, CNTf and CNTnf, respectively. Furthermore, ammonium persulfate and sodium dodecyl sulfate were incorporated to the reaction solution as dispersant and oxidizing agents, respectively. Different nanostructures such as nanoparticles or nanotubes were obtained depending on the CNT added, and characterized by scanning electron microscopy, transmission electron microscopy, UV–vis spectroscopy, infrared spectroscopy and electrochemical techniques. Spectroscopy results showed variations in the observed bands of the synthetized nanostructures attributed to changes in the molecular structures, to the state of doped PANI reached during polymerization and to the stabilization of these links by hydrogen bridge interactions. PANI and PANI–CNT composites were evaluated by electrochemical techniques to test their behavior in relation to supercapacitors properties. PANI–CNTf nanocomposites displayed improved capacitive properties in H2SO4 solutions, namely 1744 F g− 1at 2 A g− 1. Also, the specific capacitance was strongly influenced by the developed morphologies. These characteristics point to their feasible application as supercapacitors materials.