The X-ray absorption angle-dependent behavior at the potassium K-edge has been determined for two end-members and two intermediate trioctahedral micas, which are representative of the Fe2+Mg−1, Fe3+Al−1, SiAl−1FeLi−1, and F−1OH exchange vectors, using horizontally polarized synchrotron radiation. Experimental spectra are interpreted by the multiple scattering theory following decomposition according to the angular dependence approach of Brouder (1990). The experimental spectra sum up anisotropic effects deriving from in-plane and out-of-plane photoelectron interactions with the potassium near- and next-near neighbors up to the fifth/sixth coordination sphere. For the first time, the absorption edge of a low Z atom is decomposed so as to produce two partial patterns giving, respectively, the full in-plane absorption spectrum (σ||) and the full out-of-plane spectrum (σ⊥). They fully describe the complete X-ray absorption dichroic behavior of layered compounds, of which mica is a prototype. σ|| essentially reflects the arrangement of the atoms located in the mica interlayer space and facing tetrahedral sheets. Differences among the four micas depend on structural changes induced by the adaptation of their tetrahedral sheets to the increasing sizes of their octahedral sheet due to chemical substitutions (i.e., the Fe2+Mg−1 vector, mainly) and to chemical changes at the octahedral anion site (F−1OH vector). By contrast, σ⊥ reflects multiple-scattering interactions entering deep into the mica structure, beyond the tetrahedral sheet and well into the octahedral sheet. Such contributions reflect both changes in the anions coordinating the octahedral cations and increasing total amount of heavy atoms (essentially Fe), and differ based on electronic properties such as oxidation states (e.g., Fe2+ and Fe3+). Therefore, angle-dependent XANES spectroscopy is one of the rare spectroscopic techniques able not only to detect, but also to quantify structural effects in the atoms at the medium- to long-range order.