Abstract Copper(II) chloride reacts with a double-thiourea ligand tethered on a silica xerogel through a reduction-oxidation process. XPS data suggest that the main products are copper(I) chloride supported on the matrix and a tetheredcopper(II) compound containing a heterocyclic ligand derived from the double thiourea by oxidative mono-desulfurization. The presence of this anchoredcomplex is also