The 4,5-bis(diphenylphosphoranyl)-1,2,3-triazole[4,5-(P(E)Ph-2)(2)tz] derivatives of indium {kappa(3)-N,N',E-[4,5-(P(E)Ph-2)(2)-(mu-tz)]InMe2}(2) (E) O(2), S(3), Se(4) were prepared in good yield. In addition, compound 5 (E = O, E' = Se) was obtained from 4 through the replacement of a selenium atom in the P-Se(In) moiety by an oxygen atom, giving the mixed-chalcogen complex. The crystal structures of 2 and 5 exhibit a central C4In2N6O2P4 core with an almost planar arrangement (mean deviation = 0.019 and 0.042 angstrom for 2 and 0.100 angstrom for 5), while the C4In2N6S2P4 core in 3 is nonplanar (mean deviation = 0.223 angstrom).