Two decades of progress in the field of living and controlled polymerizations, combined with the elaboration of efficient conjugation reactions, have greatly contributed to the elegant preparation of functionalized macromolecular architectures.[1] However, these state-of-the-art methodologies, while providing a high degree of structural and topological control, are inadequate tools for controlling the polymer microstructure. Crucial parameters like primary structure (ie monomer sequence) and tacticity largely remain unmastered by current man-made approaches. Expectations for the next generation of synthetic polymers include performance as single chains, ability to fold and self-regulate, and ability to sense specific molecules and/or catalyze reactions.[2] These precisely functionalized linear polymers should exhibit sharply defined and tailored structure–activity relationships analogous to nature s delicately engineered macromolecules. Therefore, progress towards reliable sequence-controlled polymerization, enabling the preprogrammed distribution of multiple functional groups along the backbone, is drawing attention in a growing number of research groups worldwide.[3, 4]