Developing highly luminescent and extensively stable silver cluster‐assembled materials (SCAMs) from the inferior luminogens and unstable silver cluster is an important and challenging issue. Herein, a new luminescent three‐dimensional SCAM (Ag12CPPP, Ag12(StBu)6(CF3COO)6(CPPP)2(DMAc)12n; CPPP=2,5‐bis(4‐cyanophenyl)‐1,4‐bis(4‐(pyridine‐4‐yl)‐phenyl)‐1,4‐dihydropyrrolo3,2‐bpyrrole, DMAc=dimethylacetamide) was designed and synthesized with a quadridentate rigid emission ligand (CPPP) and a silver–chalcogenolate cluster (SCC) containing 12 AgI atoms. The luminescence study indicates that CPPP is an aggregation‐caused quenching (ACQ) molecule with twisted intramolecular charge transfer (TICT) character. Benefiting from the strong immobilization effect in the robust framework, the quantum yield of CPPP is greatly enhanced in Ag12CPPP compared with that of CPPP in solution or in the solid state. As a result, Ag12CPPP exhibits typical matrix coordination induced emission (MCIE) effect. Such efficient rigidifying methodology provides a promising approach for enhancing luminescence of ACQ molecules in an aggregated state and strengthening the silver cluster in an unstable state. Cluster lighting: Matrix coordination induced emission (MCIE) effect was observed in a new three‐dimensional silver cluster‐assembled material (SCAM). The quantum yield (QY) of the SCAM is much higher than that of the quadridentate ligand (see figure).