Hydrogen cyanide is considered as an important precursor to amino acids and nucleic acids, and its polymers could have profound implications on prebiotic chemistry. Several structures of HCN polymers are speculated, but these structures are disparate both chemically as well as structurally. Here, we employ solution-state NMR spectroscopy to investigate the structure of HCN polymers with (13)C and (15)N isotopic enrichment. From the multinuclear and multidimensional NMR investigations, we identify some discrete structural units for the most concentrated small molecular components and suggest that the dominating polymers are polyimine chain-like structures, which are formed by base-catalyzed nucleophilic addition reactions.