With Cu6I6 and Cu8I8 clusters as 5-connected nodes, a new 3-D network [Cu14I14 (dabco)5(py)] (1) (dabco = 1,4-diazabicyclo[2.2.2]octane, py = pyridine) with a two-fold interpenetrated sqp-(44.66) topology has been hydrothermally synthesized. The solid-state luminescence spectrum displays a strong yellow-light emission with λmax = 591 nm at room temperature.