Light-Induced CuAAC Reaction In article number 2100155 by Guo-Hong Ning, Dan Li, Xuanfeng Jiang, and co-workers, a novel copper-iodide cluster-based metal–organic polyhedra (MOP) with half-truncated cube topology is prepared through conformation-adaptive self-assembly strategy. This MOP containing unprecedent Cu3I3 cluster node highly exhibits photo-catalytic activity towards CuAAC reaction under the WLED irradiation in water.