A multi-anvil press was combined with monochromatic synchrotron X-ray radiation to investigate the synthesis, at high-pressure high-temperature conditions, of a recoverable bulk sample of Fe4O5, from an initial magnetite, Fe3O4, sample. Angle-dispersive diffraction patterns show that magnetite firstly breaks down, into an assemblage of hematite (Fe2O3) + Fe4O5. By increasing temperature at constant load, hematite disappears progressively by either reduction or by melting, or a combination of both. In the final product only Fe4O5 remains and, in the absence of hematite, can be kept stable and be recovered at ambient conditions. Refinement of the diffraction patterns at standard conditions demonstrate that Fe4O5 has the Sr2Tl2O5-type-structure with space group Cmcm and a = 2.8964(2) Å, b = 9.8225(6) Åand c = 12.5808(7) Å. This structure-type and related members of a homologous series, offer the possibility that the general sequence of AB(2+n)X(4+n) chemistries could, under certain conditions, be extended to accommodate prevalent oxygen fugacity or, indeed, other ordered stoichiometries through extension of the c axis by the addition of FeO6 octahedral blocks. This structural series, as in other systems, offers possibilities of hosting charge-transfer, Jahn-Teller and other electronic phenomena − as well as supporting metric distortions. Each of these possibilities is highlighted through illustration and extension to related structure-types, most notably from those of the spinels, post-spinels and post-perovskites.