Three dioxybiphenyl bridged cyclotriphosphazenes (2–4) containing the (1,1′-biphenyl)-4,4′-diol (BPD), 4,4′-sulfonyldiphenol (SDP), and 4,4′-(propane-2,2-diyl)diphenol (PDP) groups were prepared from the nucleophilic substitution reaction of hexachlorocyclotriphosphazene (1) with three different diphenols, respectively. All these compounds were structurally characterized using ESI-MS, FTIR, and NMR (1H, 31P) spectroscopies. Moreover, the molecular structures of 2–4 were unequivocally confirmed by X-ray crystallography, in which the two cyclotriphosphazene (N3P3) rings are linked via a dioxybiphenyl bridge.