Films of optically active polyaniline salts (PAN/HCSA) have been obtained by casting from solutions of emeraldine base doped with (1S)-(+)- or (1R)-(-)-10-camphorsulfonic acid (HCSA) in various solvents (NMP, DMF, DMSO or CHCl3). The mirror-imaged circular dichroism spectra for the salt films derived using (+)- and (-)-HSA, respectively, indicate enantioselectivity in the doping process. The first optically active ring-substituted polyanilines, namely poly(o-toluidine)/(+)-HCSA and poly(o-toluidine)/(-)HCSA, have also been produced in solution and as films via a similar doping procedure in DMSO.