A detailed study of the supramolecular organization of two series of peptide-based diblock oligomers is reported. The diblock oligomers are comprised of an α-helical oligopeptide rod, which is either based on γ-benzyl-L-glutamate or ε-benzyloxycarbonyl-L-lysine, and a short oligo(styrene) coil. The unique feature of these rod-coil molecules is that the conformation of the α-helical peptide rod is sensitive to temperature. As a result, the supramolecular organization of these rod-coil oligomers can be manipulated not only via changes in the block length ratio or chemical composition but also via temperature-induced conformational changes in the rod segments. This makes these molecules attractive building blocks for the development of stimuli-sensitive self-assembled materials.