Recent years have seen a dramatic increase in interest in the use of ring-opening polymerization of N-carboxyanhydride (NCA) monomers as a method to prepare well-defined polypeptides and peptide-hybrid materials. The resulting molecules are often capable of assembling into a variety of different structures, including micelles, vesicles, nanoparticles and hydrogels, and therefore have been explored as novel drug delivery systems. Peptides are attractive in this regard due to their rich chemical functionality and ability to assemble through the formation of secondary structures (for example -helices and -sheets). In addition, they are inherently biodegradable and biocompatible. This review describes recent advances in the field, covering aspects such as improved methods with which to prepare better-defined polypeptides, crosslinking of assemblies to enhance biostability, the preparation of materials that respond to a variety of stimuli (including light and intra-or extracellular redox conditions), functionalization with targeting ligands to enhance cellular uptake, assemblies for siRNA delivery and approaches to theranostic systems.3