In this work, three isostructural clusters of [Ag3Cu8(R-Ph-CC)6(N-triphos)2(Ph2PO2)3](NO3)2 (R = 4-H (1), 4-CH3 (2), 4-F (3)) were successfully synthesized and structurally determined by single crystal X-ray diffraction. At room temperature, they show weak photoluminescence in CH2Cl2 solution at ∼715 nm but with a 20-fold increase of quantum yields in their aggregation. Crystallographic and Hirshfeld surface analysis reveals a plentiful of intermolecular interactions (C−H…N, C−H…O, C−H…π, π…π) exist in their solid states, which can inhibit the intra-/inter-molecular motions (vibration and rotation) and thus generate the aggregation induced emission enhancement phenomenon. Moreover, their solid luminescent intensities at 100 K are much higher than those at room temperature. Comparisons of their luminescence show that the substituents on the para-positions of phenylethynes not only have a charge effect on emission, but also have steric effect on the molecular stacking and supramolecular interactions in the aggregated and crystalline states, and then on the aggregation-induced emission. The density functional theory (DFT) calculations show that the possible luminescence mechanism of these clusters is ligand-to-metal−metal charge transfer (LMMCT).