The purposes of this study were: (1) to review the preparation and characterization of the intergrowth between goethite and hematite crystals; and (2) to propose a schematic diagram of the epitaxial relationships among three sets of (100) goethite twin crystals associated with the (001) orientation of the hexagonal prism of hematite. The Fe(ClO4)3 solution was prepared and aged at 70°C, which precipitated goethite initially and produced hematite later with prolonged aging. Goethite and hematite aged for 20 days were observed as star-shaped and hexagonal prisms, respectively. The results suggest that hematite could form later using goethite as a template surface. A selected area electron diffraction (SAED) pattern showed the epitaxial relationship among three sets of (100) goethite intergrowth crystals and hexagonal prisms with the (001) orientation of hematite. Goethite can be produced as lath-, X-, K-, or star-shaped crystals on the (100) orientation, depending on the Fe(ClO4)3 concentrations and the addition of HClO4 to Fe solution samples which were aged for a prolonged period at room temperature. The initial solubility products [(Fe3+)(OH–)3] of the sample solution, rather than the nature of the nuclei, are the key factors governing the formation of goethite or hematite. The addition of acids and high concentrations of iron solutions extend the secondary hydrolysis and induction period (IP) and favor the formation of hematite. The index of the SAED pattern of the star-shaped goethite intergrowth twin crystal has a (100) plane parallel to this basal plane and rotates at a 60° angle between two or three sets of lath-shaped goethite crystals, which share the (011) plane and form goethite twins with ‘interpenetrated’ crystal growth. Stereoscopic viewing using Oak Ridge Thermal Ellipsoid Plot (ORTEP) and CrystalMaker software was deployed to explore the relationship and configuration of oxygen atoms between pseudo-hexagonal (100) goethite associated with hexagonal (001) hematite lattice planes. A schematic diagram of the epitaxial relationship between star-shaped (100) goethite, which is acting as a template facilitating later precipitation of (001) hexagonal prisms of hematite on it, is presented.