A new 28 membered macrocyclic ligand (1) containing N, S and Se donor atoms was prepared and structurally characterized. While in solid state the intramolecular N→Se interaction determines a contraction of the macrocycle, in solution no evidence for such an interaction was observed. The NMR spectra indicate the existence of two invertomers in the range 20–80 °C in chlorinated solvents. By reacting the macrocycle 1 with AgOSO2CF3, AgBF4 and AgPF6, respectively, the ionic species 2–4 were obtained. No major differences in the coordination pattern of the macrocyle were noted by changing the anion. The molecular structures determined by single crystal X-ray diffraction of both 2 and 3·2CHCl3 revealed a hexadentate N,S,Se coordination behavior of the folded ligand, thus resulting in a distorted octahedral environment around silver(I) in the cations. Similarly with the situation observed in 1, two of the nitrogen atoms remain coordinated to selenium. As a result of the coordination pattern, the compounds crystallize as racemic mixtures of Δ and Λ isomers.