From a basic tetrahedral Cu4I4 cluster, a new MTN-type cluster-organic framework (COZ-1) containing giant 6(4)5(12) and 5(12) cages was successfully constructed. The 6(4)5(12) cage has an inner diameter of 2.6 nm and a large pore volume of 9.2 nm(3); these tetrahedral Cu4I4 clusters with bulky size offer new opportunities for not only the formation of 4-connected zeotype structures but also the integration of porosity and photoluminescent properties from both the cluster and the framework.