The solvothermal reaction of CuCl2• 2H(2)O with pyridine-4-thiol and ethanol yielded a novel photoluminescent 3-D polymeric complex with an interesting decorated diamondoid network that is constructed of decanuclear copper(I) cluster units and μ(4)-Cl ligands. The in situ generation of CuSO4• 5H(2)O implies the spontaneous occurrence of desulfurization and redox reactions in the present system.