Conductive polyaniline solutions were chemically prepared using bis(2-ethylhexyl)hydrogen phosphate (DiOHP) as the dopant chemical species. The codissolution method leads to conductive polyaniline-polystyrene (PANI-PSt) composites with good mechanical properties. The electronic structure of both conducting PANI films and PANI-PSt blends was investigated by X-ray photoelectron spectroscopy, which allowed one to quantify the proportion of benzenoid amine, quinoid imine, and protonated units. Blending polyaniline with PSt does not involve important modifications in the polymer electronic structure.