Hydrogen-bonded supramolecular polymers were prepared from the derivatives of alpha-amino-epsilon-caprolactam (ACL), obtained from a renewable resource. Several self-complimentary bis- or tetra-caprolactam monomers were synthesized by varying the number of carbons of the spacer between the hydrogen-bonding end groups. Physical properties of these hydrogen-bonded polymers were clearly demonstrated by differential scanning colorimetry, solid-state NMR, and X-ray powder diffraction analyses. The supramolecular behavior was also supported by fiber formation from the melt for several of these compounds, and stable glassy materials were prepared from the physical mixtures of two different biscaprolactams. The self-association ability of ACL was also used by incorporating ACL at the chain ends of low-molecular weight Jeffamine (M(n) = 900 g/mol) using urea and amide linkages. The transformation of this liquid oligomer at room temperature into a self-standing, transparent film clearly showed the improvement in mechanical properties obtained by the introduction of terminal hydrogen-bonding groups. Finally, the use of monomers with a functionality of four gave rise to network formation either alone or combination with bifunctional monomers. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 2451-2460, 2011