This article discusses the characterization of gray iron structures, following the sequence of structure formation, as it applies to unalloyed or low-alloyed gray iron. Austenite grains are the basic crystallographic entities of the metallic matrix in gray cast iron precipitated from the liquid melt. The article describes the macrostructure and dendrite morphology of primary austenite. Eutectoid transformation in the solid state causes the transformation of austenite to pearlite and/or ferrite, producing the as-cast structure. The article discusses the observations of the graphite and ferritic/pearlitic structure in as-cast gray iron.