Dynamic covalent chemistry (DCC) is a powerful strategy for assembling complex molecular architectures under thermodynamic control. In this talk, I will discuss our latest results1 for RNA synthesis using DCC. Thermodynamically controlled RNA hairpin synthesis is achieved with high selectivity and yields. This high selectivity allows orthogonal RNA systems to “self-sort” exclusively into their respective hairpins without cross-ligation. These findings showcase RNA DCC as a versatile synthetic strategy, promising future applications ranging from modular synthesis of functional RNAs to models for the emergence of early genomes.