A novel non-interpenetrated 2D coordination polymer [Cu4I4(DACH)2]n bridged by the flexible trans-1,4-diaminocyclohexane (DACH) ligand has been synthesized under hydrothermal condition and characterized by single crystal X-ray diffraction, TG–DTA and the solid-state luminescence spectrum. In the compound, each Cu4I4 cluster is bridged by DACH ligand to form a quadrate-grid 2D network with the inner cavities of approximate size of 6.35×18.12Å. It is unusual that these 2D networks are stacked and there exist the N–H…I hydrogen bonds between layers. The channels are finally formed along b-axis with small size of cavities. Thermal analysis shows that the complex is stable up to ca. 240°C. The solid-state luminescence spectrum displays a strong yellow emission band at room temperature, characteristic of the Cu4I4 cluster centers.