The processability of conductive polymers such as polyaniline (PANI) still poses a challenge due to their properties. The use of stabilizers, compatible and able to interact with PANI, to obtain dispersible and stable colloids is described in this work. To this aim, potato starch has been used as a steric stabilizer for the preparation of polyaniline (emeraldine salt, ES)/starch biocomposites, by exploiting oxidative polymerization of aniline in aqueous solutions containing different ratios of aniline and starch (% w/w). The polyaniline/starch biocomposites were subjected to structural and spectroscopic analyses, thermal analysis, morphological analysis and electrochemical analysis. The samples were then tested for their dispersibility/solubility in various organic solvents. The results showed the formation of PANI/starch biocomposites with an overall smaller size than starch particles, with improved aqueous dispersion and solubility in organic solvents. Although X-ray diffraction and differential scanning calorimetry analyses indicated a loss of crystallinity in the biocomposites, the cyclic voltammetry tests showed that all PANI ES/starch biocomposites display improved redox exchange properties.