The chirality organization of polyaniline-unit molecules was achieved by the introduction of amino acid pendant groups through intramolecular hydrogen bonding, which plays an important role in the stabilization of the chirality-organized redox species. Another interesting feature of the synthesized polyaniline-unit molecules is the luminescent switching properties based on the redox states of the phenylenediamine moiety. Getting organized: The chirality organization of polyaniline-unit molecules was achieved by the introduction of pendant amino acid groups through intramolecular hydrogen bonding; these groups play an important role in the stabilization of the chirality-organized redox species. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.