A novel isolated cluster-based iodocuprate [Cu(1,10-phen)3]2[Cu11I15] (1) was successfully constructed with in situ generated [Cu(1,10-phen)3]2+ cation as the charge balancer and structural directing agent. In compound 1, the linkage of Cu(I) and I- generated an anionic [Cu3I4] building unit, and alternate connection of these moieties with each other further gave rise to a bowknot-like high-nuclearity Cu-I cluster. By virtue of the intermolecular forces, a three-dimensional supramolecule was finally fabricated with the transition metal complex as the template and guest species. A short Cu-Cu distance could be observed, suggesting the existence of closed-shell d10-d10 cuprophilic interaction in the structure of 1. Interestingly, the photocatalysis experiment has been performed on solid 1, which implies that the title compound could be acted as a promising visible light driven photocatalyst for the degradation of the organic dye indigo carmine (IC). In addition, the mechanism for the photodegradation process has been discussed in detail.