A crystal-chemical study of trioctahedral micas previously characterized by single-crystal XRD has been performed by XANES spectroscopy at the Si and Al K edges. XANES, being a local structural probe, can investigate distortion and modification of the tetrahedral sheet with increasing Fe for Mg substitution in the octahedral sheet. Comparison of XANES spectra allows determining the size of the tetrahedral site occupied by either Si or Al. The Si-O distance remains essentially unchanged whereas the Al-O distance appears to increase. The behavior may be interpreted as a tilt of the tetrahedra, initially rotated to match the ideal mica geometry, with increasing Fe substitution in the octahedral sheet.