AbstractHexakis (2‐halo‐anilino) cyclotriphosphazenes (2‐X‐C6H4NH)6P3N3 {X = F (1d), Cl (1e), Br (1f)} were prepared by refluxing mixtures of hexachloro cyclotriphosphazene, 2‐haloaniline and triethylamine in toluene and characterized by single crystal X‐ray diffraction. 1d, 1e and 1f were reacted with nBuLi in thf. Reactions were monitored with 31P NMR. Addition of three equivalents of nBuLi yields lithium complexes of trianionic phosphazenates [{(thf)2Li}3{(2‐X‐C6H4N)3(2‐X‐C6H4NH)3P3N3}] {X= F (2d), Cl (2e) and Br (2f)}. 2d, 2e and 2f were structurally characterized by X‐ray diffraction, which reveals monomeric cis‐metalated phosphazenates featuring central P3N3 ring systems of chair conformation. Lithium ions reside in three N(eq)‐P‐N(endo) chelation sites at one face of the P3N3 ring system. Li…X distances are rather long (> 3Å) indicating no Li‐X interactions.