Charge-transfer complexation of iodine with a new benzo-substituted macrocyclic diamide 5, 6,7,8,9,10-hexahydro-2H-1,13,4,7,10-benzodioxatriazacyclopentadecine-3,11(4H,12H)-dione (L) with iodine was studied spectrophotometrically in chloroform, dichloromethane and their 1:The observed time dependence of the charge-transfer band and subsequent formation of I 3 -ion are related to the slow formation of the initially formed 1:1 L.I 2 outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion, as follows: L + I 2 o L.I 2 (outer complex), fast L.I 2 (outer complex) o (L.I + )I -(inner complex), slow (L.I + )I -(inner complex) + I 2 o (L.I + )I 3 -, fastThe pseudo-first-order rate constants for the transformation process were evaluated in different solvent systems. The stability constants of the resulting EDAr complexes were also evaluated and the solvent effect on their stability is discussed. The resulting complexes were isolated and characterized by FTIR and 1 H NMR spectroscopy.