The influence of iron on the formation of Al–Mn–Fe intermetallic compounds (IMCs) has been investigated in the solidification of Mg–9Al-0.7Zn-0.2Mn (wt.%, AZ91) with iron contents ranging from ∼0.001 to > 0.01 wt.% Fe. Four Al–Mn–Fe IMCs formed depending on the Fe-content and location in the crucible: B2–Al(Fe,Mn), Al8Mn5, Al11Mn4 and, at the bottom of crucibles, Al5Fe2. The four IMCs nucleated and grew on one another, producing multiphase particles. These usually contained numerous orientations that were all interrelated through simple orientation relationships that are discussed in terms of the similarities between the IMC crystal structures. The iron content affected the IMC phase fractions and the multiphase particle morphology. At low iron content, the Fe-rich B2 phase was encapsulated by a low-Fe Al8Mn5 shell. With increasing iron content, the Fe-rich phases (B2 and Al5Fe2) gradually became in direct contact with the α-Mg. The threshold Fe:Mn content for adequate corrosion performance is found to correlate approximately to where B2–Al(Fe,Mn) first becomes exposed to the α-Mg matrix.