The stable ϕ phase that forms below ∼923 K around the Al69.2Cu20.0Cr10.8 composition was found to be hexagonal [P63, a = 11.045 (2), c = 12.688 (2) Å] and isostructural to the earlier reported Al6.2Cu2Re X phase [Samuha, Grushko & Meshi (2016). J. Alloys Compd.670, 18–24]. Using the structural model of the latter, a successful Rietveld refinement of the XRD data for Al69.5Cu20.0Cr10.5 was performed. Both ϕ and X were found to be structurally related to the Al72.6Cu11.0Cr16.4 ζ phase [P63/m, a = 17.714, c = 12.591 Å; Sugiyama, Saito & Hiraga (2002). J. Alloys Compd.342, 148–152], with a close lattice parameter c and a τ‐times‐larger lattice parameter a (τ is the golden mean). The structural relationship between ζ and ϕ was established on the basis of the similarity of their layered structures and common features. Additionally, the strong‐reflections approach was successfully applied for the modeling of the ϕ phase based on the structural model of the ζ phase. The latter and the experimental structural model (retrieved following Rietveld refinement) were found to be essentially identical. [ABSTRACT FROM AUTHOR]