We report on the synthesis, crystal, and electronic structure, as well as the magnetic, and electric properties of the phosphorus‐containing tantalum nitride P1–xTa8+xN13 (x = 0.1–0.15). A high‐pressure high‐temperature reaction (8 GPa, 1400 °C) of Ta3N5 and P3N5 with NH4F as a mineralizing agent yields the compound in the form of black, rod‐shaped crystals. Single‐crystal X‐ray structure elucidation (space group C2/m (no. 12), a = 16.202(3), b = 2.9155(4), c = 11.089(2) Å, β = 126.698(7)°, Z = 2) shows a network of face‐ and edge‐sharing Ta‐centered polyhedra that contains small vacant channels and PN6 octahedra strands. Atomic resolution transmission electron microscopy reveals an unusual P/Ta disorder. Mixed‐valent tantalum atoms exhibit interatomic distances similar to those in metallic tantalum, however, the electrical resistivity is quite high in the order of 10‑1 Ω cm. The density of states and the electron localization function indicate localized electrons in both covalent and ionic bonds between P/Ta and N atoms, combined with less localized electrons that do not contribute to interatomic bonds.