A series of copper(II) thiosulfonate complexes have been prepared via the reaction of [Cu(Me(3)tren)(OH2)](ClO4)(2) (Me(3)tren = tris(2-methylaminoethyl)amine) with three thiosulfonate ligands (RSO2S-, where R = Me, Ph, and MePh) and characterized by microanalysis, FTIR spectroscopy, and X-ray crystallography. In these complexes, the distorted trigonal bipyramidal copper(II) coordination sphere is occupied by four amine nitrogen atoms from the tripodal tetramine ligand and an apically bound sulfur atom from the thiosulfonate ligand. By using the tripodal tetramine ligand the oxidation of the thiosulfonate has been restricted, allowing the isolation of the complexes. The Cu-S distances were found to be similar to those in related thiosulfate complexes, indicating coordinative interactions of similar strength. Two types of intramolecular hydrogen bonding interactions were evident which enhance the binding of the thiosulfonate to the copper(II) center. These interactions, which involve two amine N-H groups and either one or two thiosulfonate oxygens, were found to be weaker than in the corresponding thiosulfate complexes. The complex formation constants for the thiosulfonate complexes (log K-f = 0.3-0.7) were found to be two orders of magnitude lower than compared to the thiosulfate analogues. This correlates well with a lower strength of intramolecular hydrogen bonding.