In this work we analyse the polarized Mg and Fe K‐edge XANES spectra obtained on single crystals of phlogopite, (sample from Franklin, New Jersey), and of tetra‐ferriphlogopite (sample from Tapira, Alto Paranaiba, Brazil). These crystals show composition close to the end‐members, thus they present similar chemical composition in octahedral and interlayer position, but they differ for tetrahedral substitutions. Our aim is thus to discover the influence of the different chemical composition of the T sheet on the M sheet topology. To reach this goal, as the differences observed in the XANES spectra when changing the beam incidence angle are associated with the different contributions of the photoelectron pathways involving the absorber atom and its near and next‐near‐shell neighbours in the direction of the electric field vector, we investigated the angular dependence of the spectral XANES features at the Mg and Fe K edges.