The marriage of metal-organic framework (MOF) and metal halide gives birth to a novel 3D cationic MOF, [Co(tib)2]·[Cu4I6] (1, tib = 1,3,5-tris(1-imidazolyl)benzene), templated by anionic iodocuprate cluster (CuI4I62-). 1 features a (3,6)-connected network with CoII 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 halometallate-directed 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.