Reorganization of Self‐Assembled DNA‐Based Polymers using Orthogonally Addressable Building Blocks**

Abstract Nature uses non‐covalent interactions to achieve structural dynamic reconfiguration of biopolymers. Taking advantage of the programmability of DNA/DNA interactions we report here the rational design of orthogonal DNA‐based addressable tiles that self‐assemble into polymer‐like structures that can be reconfigured by external inputs. The different tiles share the same sticky ends responsible for self‐assembly but are rationally designed to contain a specific regulator‐binding domain that can be orthogonally targeted by different DNA regulator strands. We show that by sequentially adding specific inputs it is possible to re‐organize the formed structures to display well‐defined distributions: homopolymers, random and block structures. The versatility of the systems presented in this study shows the ease with which DNA‐based addressable monomers can be designed to create reconfigurable micron‐scale DNA structures offering a new approach to the growing field of supramolecular polymers.