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AgI/CuI bimetallic clusters have been widely reported, but synthesis of such clusters via simple selfassembly of heterometallic ions in air remains challenging due to the susceptibility of CuI ions to oxidation. In this study, protected by the phenylacetylene auxiliary ligand, we utilized [Cu(CH3CN)4]PF6 in conjunction with the (iPrSAg)n polymer to form Ag(I)-Cu(I) oligomer precursors, serving as the starting point for constructing a new [Ag11-xCux(iPrS)9(DPPM)3](PF6)2 cluster (DPPM = bis(diphenylphosphino) methane, Ag11-xCux, x = 5-9). When the (iPrSAg)n precursor was replaced by (tBuSAg)n, another cluster [Ag21Cu4S2(tBuS)18(CH3CN)4](CH3OH)2(H3O)(PF6)4 (Ag21Cu4) was obtained. By combining crystallographic data and electrospray ionization mass spectrometry (ESI-MS) results, the compositions and structures of these two new clusters were determined. Additionally, the optical physical properties of the luminescent Ag11-xCux were investigated, showing red phosphorescence emission in both solid-state and solution phases. The solid-state phosphorescence quantum yield (QY) is 8%, with a lifetime of 7.2 µs. These findings suggest that phenylacetylene auxiliary ligands can effectively stabilize CuI ions and guide the assembly of silver-copper bimetallic thiolate motifs into new compounds under ambient conditions. [ABSTRACT FROM AUTHOR]