Aurivillius phases is summarized in the composition map in Fig. , where the Mn concentration varies from 0.60 to 0.75, complementing the modelled XRD data in Table . This observation of structural reorganization into a higher-layered m = 6 Aurivillius phase to accommodate increased magnetic fraction is particularly interesting. At large values of m, the free energy of formation in Aurivillius phases becomes thermodynamically degenerate, making the synthesis of higher layered (m > 5) homologues challenging. These phases are typically difficult to achieve without the support of epitaxial substrates or kinetically controlled growth conditions. This work progresses previous studies by Sun et al. The m = 7 Sr4Bi4Ti7O24 phases were synthesized in the kinetic limit using pulsed laser deposition on epitaxial (SrTiO3 (001)), LaAlO3 (001)c, and SrRuO3 (001)c/SrTiO3 (001)) substrates. Alternatively, the work presented in this contribution demonstrates that using transition metal cations for aliovalent substitution in straightforward chemical solution deposition processes can overcome thermodynamic challenges in synthesizing higher-layered Aurivillius homologues. This approach has eliminated the need for epitaxial substrates or kinetically limited growth processes for this Bi/Ti/Mn/Fe-based material system.