The synthesis and characterization of polymers derived from isocyanopeptides are described. Optically pure dipeptides based on alanine and glycine were equipped with an isocyano function and subsequently polymerized with a Ni(II) catalyst. Infrared and NMR spectroscopy indicated that the side chains of the polymers were connected by well-defined arrays of intramolecular hydrogen bonds. The weight-average molecular weights of the polymers were determined by atomic force microscopy to be 200-400 kg/mol (polydispersity index = 1.4-1.7).