Described herein is a comprehensive survey on the most recent advancements in polycarbodiimide synthetic methodologies, structure determination, property design, and self-assembly. In particular, the N-15-isotopic enrichment of polycarbodiimides is detailed along with the use of N-15 NMR to identify the regioregularity and mechanism of chiroptical switching in polycarbodiimides. Furthermore, the new Ni(II) mediated "living" polymerization is explained along with its utilization in the incorporation of polycarbodiimides into block copolymers, graft copolymers, and star polymers. Finally, we review the recent discoveries focusing on the highly tunable self-assembly behaviors of polycarbodiimide homopolymers and copolymers. (C) 2017 Wiley Periodicals, Inc.