Calix[4]bis(thiacrown-5) (L) with 1,3-alternating conformation was employed as a strong dinucleating ligand for the soft metal ions Ag-I and Cu-I. The reaction of L with AgPF6 afforded a discrete endo-coordinated disilver(I) complex 1, [Ag-2 L](PF6)(2). In contrast, mixed products (2a + 2b) consisting of 3D networks were obtained from the reaction of L and CuI; 2b linked with a Cu4I4 cubane unit was shown to generate photoluminescence, while 2a linked with a Cu2I2 rhomboid unit does not.