The marriage of metal-organic framework (MOF) and metal halide gives birth to a novel 3D cationic MOF, [Co(tib)(2)]center dot[Cu4I6] (1, tib = 1,3,5-tris(1-imidazolyObenzene), templated by anionic iodocuprate cluster ((Cu4I62-)-I-1). 1 features a (3,6)-connected network with Co-II and tib moieties as six-connected and three-connected. nodes, respectively. It is notable that the template (iodocuprate cluster) in 1 is distinct from the widely utilized species such as organic solvents, ionic liquids, organic amines, and surfactants. This Communication provides a new avenue to fabricate halometallatedirected MOF via incorporating halometallate into MOF. The photocatalytic activity toward the degradation of methyl orange in aqueous solution under visible-light irradiation has also been studied.