AbstractThe five-layer Aurivillius phase Bi₆Ti_xFe_yMn_zO₁₈ system is a rare example of a single-phase room temperature multiferroic material. To optimise its properties and exploit it for future memory storage applications, it is necessary to understand the origin of the room temperature magnetisation. In this work we use high resolution scanning transmission electron microscopy, EDX and EELS to discover how closely-packed Ti/Mn/Fe cations of similar atomic number are arranged, both within the perfect structure and within defect regions. Direct evidence for partitioning of the magnetic cations (Mn and Fe) to the central three of the five perovskite (PK) layers is presented, which reveals a marked preference for Mn to partition to the central layer. We infer this is most probably due to elastic strain energy considerations. The observed increase (>8%) in magnetic cation content at the central PK layers engenders up to a 90% increase in potential ferromagnetic spin alignments in the central layer and this could be significant in terms of creating pathways to the long-range room temperature magnetic order observed in this distinct and intriguing material system.