The various microstructures of cast irons are reviewed, including carbidic and graphite forms (flake, compacted, spheroidal, and undercooled, etc.), exploring whether the presence of externally introduced defects in the form of oxide double films (bifilms) in suspension in melts seem to provide, for the first time, a uniform explanation for all the structures and their properties. Silica-rich oxide bifilms provide the substrates on which oxysulfide particles form, nucleating graphite. The presence of the film provides the favored substrate over which graphite grows, which leads to the development of flake graphite. The addition of limited Mg to form compacted graphite destroys all but a remnant of the silica-rich bifilms. The oxide film remnant is stabilized by the presence of the graphite nucleus, which causes the graphite to grow unidirectionally in a filamentary form. The addition of excess Mg destroys all traces of the oxide bifilms, leaving only the original nuclei, around which graphite is now free to entirely enclose, initiating the spherical growth mode. Undercooled graphite is the true coupled growth form, nucleated at even lower temperatures in the absence of favorable film substrates in suspension; the graphite adopts a continuous growth mode in a matrix of austenite. Carbides in mottled and white irons form on the oxide bifilms that often lie along grain and interdendritic boundaries, which explains the apparent brittleness of these strong, hard phases. In most cases of non-spheroidal growth modes (flake and misshaped spheroids), it is proposed that the impairment of the mechanical properties of irons is not strongly determined by graphite morphology but by the presence of oxide bifilms. Spheroidal graphite iron has the potential for high properties because of the absence of bifilms.