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Coordination compounds have undergone booming development in the past 20 years for their applications as multifunctional materials in the field of catalysis and biomedicine. To create compounds with both catalytic and bioactive properties, we selected Cu(II) ion and benzimidazole (Hbim) ligand as the building blocks to fabricate a new cluster-based Cu(II) compound [Cu4OCl6(Hbim)4]n·n(H2O)·2n(EtOH) (1). The exploration of single crystal X-ray diffraction exhibits that complex 1 is a 0D isolated structure on the basis of tetrahedral {Cu4O} clusters. Moreover, such supramolecular framework not only shows excellent photocatalytic effect for the MB photodegradation under the irradiation of ultraviolet light but also has the application values against orbital wall fracture. This work gives new insights on the creation of coordination polymers which might be potentially used as photocatalytic and bioactive reagents.