The metal ion-binding properties of two 27-membered macrocycles with N2S5O2 donor atoms 1 and 2 were investigated using solvent extraction experiments. In order to explain complexation behavior of macrocycles, extraction of ions in the interfacial region of liquid-liquid phase was modeled by Langmuir adsorption isotherm. The macrocycles 1 and 2 extracted Ag+ metal ion up to 95% to the dichloromethane and chloroform phase effectively. The Ag+ ion adsorption capacities of macrocycles 1 and 2 were obtained as 75% and 98% at 20 degrees C, respectively.