The synthesis and supramolecular organization of a novel class of rod-coil type diblock oligomers will be discussed. The diblock oligomers consist of a rodlike alpha -helical oligopeptide segment that is conjugated to an oligo(styrene) coil. In comparison with most of the rod-coil type oligomers that have been investigated so far, these peptide-based diblock oligomers possess some unique features: (i) the conformation of the oligopeptide rod segment can be reversibly manipulated under the action of appropriate external stimuli, and (ii) the self-assembly of these molecules is (also) driven by directed hydrogen-bonding interactions. The diblock oligomers are prepared by ring-opening polymerization of gamma -benzyl-L-glutamate N-carboxyanhydride using a primary amine-terminated oligo(styrene) as the initiator. The diblock oligomers form thermotropic liquid-crystalline phases, whose supramolecular organization depends both on the relative block-lengths and on the conformation of the peptide segment.