The self-assembly of well-defined organic organometallic polystyrene-b-poly(ferrocenylmethyl(dimethylaminopropynylsilane)) (PS-b-PFAMS) diblock copolymers has been systematically investigated by varying the volume fraction of the organometallic block (PFAMS). Quaternization of the PFAMS block yielded PS-b-qPFAMS, which was ionically complexed to the anionic surfactants sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and sodium bis(2,2,3,3,4,4,5,5,S-nonafluoropentyl) sulfosuccinate (AOT(F)). The self-assembly of the block copolymer-surfactant complexes was also studied in bulk and thin films and produced materials with structural hierarchy over multiple length scales as shown by AFM, TEM, and SAXS studies.