Reaction of the m-terphenyldichlorophosphanes 2,6-(2-MeC6H4)(2)C6H3PCl2 (1), 2,6-(4-t-BuC6H4)(2)C6H3PCl2 (2), or 2,6-Mes(2)C(6)H(3)PCl(2) (3) with excess NaN3 in acetonitrile at room temperature afforded the corresponding bisazidophosphanes 2,6-(2-MeC6H4)(2)C6H3P(N-3)(2), 2,6-(4-t-BuC6H4)(2)C6H3P(N-3)(2) (5), or 2,6-Mes(2)C(6)H(3)P(N-3)(2) (6) (Mes = 2,4,6-Me3C6H2), respectively. These compounds are thermally labile and decompose into a number of azidophosphazenes. The azidocyclophosphazenes [NP(N-3)(C6H3(4-t-BuC6H4)(2)-2,6)](3) (4) and [NP(N-3)C(6)H(3)Mes(2)-2,6](2) (8) have been isolated from these mixtures. All compounds were characterized by H-1, C-13, P-31 NMR and IR spectroscopy. Crystal structures of 2, 4, and 8 were determined.