Reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6 1, with sodium aryloxides have been studied. Compound 1 was found to react by the nucleophilic substitution pathway to yield monocyclophosphazenes [N3P3Cl6(OC6H2Bu13‐2,4,6) 5 and N3P3Cl4(OC6H2Me‐4‐Bu12‐2,6)2 6] and bi(cyclophosphazenes) ([Cl5N3P3‐P3N3Cl4(OC6H3Bu12‐2,6)] 7 and [N3P3(OC6H3Bu12‐2,6)5]2 8). The unusual bi(cyclophosphazenes) 7 and 8 are the first examples of two cyclotriphosphazene rings linked by a P(SINGLE BOND)P bond [2.193 (2) Å], which have been obtained by reacting 1 with ArONa. The structures of compounds 5–8 are ascertained by elemental analyses, 1H‐, 31P‐13C‐NMR, IR, and MS spectra. The molecular structure of monocyclic‐phosphazene 5 was determined by X‐ray diffraction techniques for further structural assignment. It crystallizes in the monoclinic space group P21/m with a = 6.144(2), b = 17.079(9), c = 13.181(9) Å, β = 92.79(7), and Z = 2, R = 0.074. Compound 5 is on a crystallographic mirror plane, and there is only a half molecule in the asymmetric unit. © 1996 John Wiley & Sons, Inc.