Ferrocenylmethyl methacrylate (FMMA) is one of the very few metallocene‐based monomers that are promising candidates for truly living anionic polymerization. Nevertheless, FMMA homopolymers with a narrow polydispersity, or block copolymerization studies that result in satisfying blocking efficiencies, are unknown so far. Here we describe a procedure that leads to highly regular FMMA‐based polymers for the first time, characterized by polydispersity indices (PDI) of less that 1.05 and very high blocking efficiencies (>95%) in sequential copolymerization with styrene. Some of the obtained polystyrene‐block‐(ferrocenylmethyl methacrylate)]s show unusual microphase morphologies, presumably the consequence of high Tgs causing ‘frustrated’ non‐equilibrium states.
