A series of poly(styrene-block-ferrocenyldimethylsilane) copolymers (SF) with different relative molar masses of the blocks were prepared by sequential anionic polymerization. The bulk morphology of these polymers, studied by TEM and SAXS, showed well-ordered lamellar and cylindrical domains as well as disordered micellar structures. Temperature-dependent rheological measurements exhibited an order-disorder transition for SF 17/8 (the numbers refer to the relative molar masses in 103 g/mol) between 170 and 180°C, and an order-order transition for SF 9/19 between 190 and 200°C. The morphologies of binary blends of the diblocks with homopolymer were also investigated. In the blends the molar mass of the homopolymer was always less than the molar mass of the matching block. Ordered spheres on a bcc lattice and double-gyroid morphology were observed for the blends. The double-gyroid morphology was found only in F-rich diblock/homopolymer systems.