Aniline matrix polymerization in the presence of polysulfonic acids with different chemical structure and molecular mass in water and water-2-propanol mixtures is investigated. It is found that aniline matrix polymerization leads to formation of soluble polyelectrolyte complexes where polyaniline is in emeraldine form. The dimensions of polyaniline-polyelectrolyte complex particles do not depend on the molecular mass and chemical structure of polyelectolyte in water. Obtained complexes are stabilized not only with electrostatic but also with non-ionic, e.g. Van der Waals’ interactions. The proton conductivity of polyelectrolyte complexes of PANI-MF-4SK is investigated and it is found the proton conductivity can be controlled with varying of ANI amount in the initial reaction mixture.