In inorganic electrides, free electrons usually occupy empty spaces surrounded by irreducible cations such as alkali earths. Here, we report on the unique hybridization of interstitial electrons with Mn/Fe d orbitals in certain known A₆MN₅ compounds. Calculations show these electrons reside in axial positions 1.83 Å from the metal of [MN₃] (M = Mn, Fe) units, resulting in a trigonal bipyramidal [MN₃(e^–)₂] unit. Despite the metal proximity, the oxidation state of Mn and density of states in comparison to related Ca₃MnN₃ and Ba₃MnN₃ calculations show this localization to be of distinct electrons, rather than metal nature. Partial density of states and group theory show that, unlike hydride, the interstitial electron ligand can hybridize not only with metal d_z2 but also with d_xz and d_yz orbitals by using mixed electride 2s-2p states. These findings help us understand new properties such as magnetism from anionic electrons within rich transition metal chemistry.