We have examined the preferred 3D structure of homopeptides based on an α-amino acid lacking the asymmetry at the α-carbon but exhibiting chirality in the side chains (at the two β-carbons). These joint stereochemical properties are remarkably unusual for an α-amino acid. To this end, we carried out an experimental investigation by X-ray diffraction and NMR spectrometry. The results point to a well-defined relationship between screw sense of the turn and helix structures formed and side-chain configurations.