Polyaniline salts are being prepared with the use of acids by the oxidation of aniline using ammonium persulfate. The aim of this work is to avoid the use of acids in the preparation of a polyaniline salt, which is acidic in nature. The synthesis was carried out by the oxidation of ammonium persulfate in the presence of alcohol, β-naphthol, without using any acids. This novel polyaniline salt contains dual dopants of β-naphthol and sulfuric acid. The sulfuric acid group was generated from ammonium persulfate during the oxidation of aniline. This synthesis procedure gave nanosized fibers of a polyaniline salt having crystalline nature with optoelectronic and fluorescence properties.