Attachment of chiral azobenzene chromophores to plasmachemical deposited structurally well-defined nanolayers yields supramolecular chiroptical properties. In the case of (S)-3-methyl-3-amino-1-(4′-cyano-4-azobenzene)pyrrolidine derivatized pulsed plasma poly(glycidyl methacrylate) nanofilms, circular dichroism measurements demonstrate enantiomeric toggling (switching) and longevity of chiroptical performance, which can be attributed to stable supramolecular helical configurations.