Selected ternary compounds of the family of AT6X4 (LiCo6P4‐type) intermetallics were studied by ab initio methods with respect to their electronic structures and chemical bonding. The bonding characteristics highlight the role of the three‐dimensional [T6X4] polyanionic networks which, within the hexagonal channels, accommodate loosely bonded A cations. In alkali metal based compounds, when T is replaced by indium (e.g. in KIn6Au4) the reverse occupancy leads to positively charged In (ca. +0.5) and negatively charged Au (ca. –0.9). Peculiar magnetic behavior is traced out whereby a magnetic order is identified only when T is a 3d element, which polarizes and induces a negative small moment on A (U) as in UCr6P4 oppositely to CeRh6X4 for X = Si, Ge.