Programmable and decodable synthetic polymer architectures through DNA-templated assembly

The properties of synthetic polymers are encoded in their molecular architecture, yet no general framework exists to systematically control or decode that architecture. This gap has left vast regions of polymer design space unexplored, limiting the discovery of materials with tailored properties. Here, we establish DNA as a molecular programming language for synthetic polymers. Sequence-defined scaffolds direct diverse polymer blocks into programmable architectures including linear, star, and graft, decoupling spatial organization from chemical synthesis. In star architectures, programmed arm placement translates ionic strength into architecture-dependent shifts in spatial organization and rigidity. In graft architectures, DNA barcodes enable one-pot assembly and sequence-resolved decoding of arm placement in complex mixtures. These results establish a framework in which DNA programs, diversifies, and decodes the architecture of synthetic matter, accelerating discovery across materials science and medicine.