X-ray photoelectron spectroscopy (XPS) has been employed to investigate the protonation degree of polyaniline doped with sulfosalicylic acid (PAni-SSA) obtained by different synthetic methods. The protonation degree has been compared to electrical conductivity. Prepared PAni-SSA through the redoping process in an agate mortar displays conductivity values within the range of 1S/cm. Protonation degree of synthesized PAni-SSA by aqueous dispersion polymerization of aniline in the presence of SSA is higher than 50 %, indicating that a substantial portion of amine units have also been protonated. The C/N and S/N molar ratios obtained by XPS analysis indicate that the polyaniline chains obtained by aqueous dispersion polymerization are protonated by both sulfate anions.