Polyferrocenylsilanes (PFSs) are a class of transition metal-containing polymers consisting of alternating ferrocene and organosilane units that have become readily available via the living anionic ring-opening polymerization (ROP) of monomeric silicon-bridged [1]ferrocenophanes. The discovery of living anionic ROP of sila[1]ferrocenophanes has not only yielded polyferrocene polymers with controlled molecular weight and low PDIs, but also, has allowed for access to a new class of block copolymers with transition metal centres in the main chain of one of the blocks. To date, PFS-based block copolymers remain the most extensively studied class of metallopolymers and have recently found utility in materials science. PFS block copolymers would be expected to self-assemble in selective solvents for one of the blocks to form polymeric micellar aggregates. The study of micellization behaviour to yield cylindrical micelles, has revealed that crystallization of PFS block is the driving force for the formation of semicrystalline cylindrical micelles.