A tetra-armed cyclen bearing two benzo-15-crown-S ethers in the side arms (1) is reported. When 1 equiv of Ag+ is added to 1, the aromatic side arms cover the Ag+ incorporated in the cyclen. Upon the addition of more than 1 equiv of Ag+ to 1, the cyclen moiety binds Ag+ first, before the crown ether in the side arms subsequently binds Ag+. The log K-11 log K-12, and log K-13 values for the 1:1, 1:2, and 1:3 (=1/Ag+) complexes were estimated to be 9.4, 5.8, and 4.0, respectively. We found that the tetra-armed cyclen possessing crown ethers in the side arms behaves like an argentivorous molecule even though the crown ether arms bind metal cations.