A series of Ag-1-Cu-1 heteronuclear alkynyl complexes were prepared by reaction of polymeric (MC=CC6H4R-4)(n) (M = Cu-1 or Ag-1; R = H, CH3, OCH3, NO2, COCH3) with [M'(2)(mu-Ph2PXPPh2)(2)(MeCN)(2)](ClO4)(2) (M' = Ag-1 or Cu-1; X NH or CH2) Heterohexanuclear complexes [Ag4Cu2(mu-Ph2PNHPPh2)(4)(CdropCC(6)H(4)R-4)(4)](ClO4)(2) (R = H, 1; CH3, 2) were afforded when X = NH, and heterooctanuclear complexes [Ag6Cu2(mu-Ph2PCH2PPh2)(3)(CdropCC(6)H(4)R-4)(6)(MeCN)](ClO4)(2) (R = H, 3; CH3, 4; OCH3, 5; NO2, 6) were isolated when X = CH2. Self-assembly reaction between (MCdropCC(6)H(4)COCH(3)-4)(n) and [M'(2)(mu-Ph2PCH2PPh2)(2)(MeCN)(2)](ClO4)(2), however, gave heterohexadecanuclear complex [Ag6Cu2(mu-Ph2PCH2PPh2)(3)(CdropCC(6)H(4)COCH(3)-4)(6)](2)(ClO4)(4) (7). The heterohexanuclear complexes 1 and 2 show a bicapped cubic skeleton (Ag4Cu2C4) consisting of four Ag-1 and two Cu-1 atoms and four acetylide C donors. The heterooctanuclear complexes 3-6 exhibit a waterwheel-like structure that can be regarded as two Ag3Cu(CdropCC(6)H(5))(3) components put together by three bridging Ph2PCH2PPh2 ligands. The heterohexadecanuclear complex 7 can be viewed as a dimer of heterooctanuclear complex [Ag6Cu2(mu-Ph2PCH2PPh2)(3)(CdropCC(6)H(4)COCH(3)-4)(6)](ClO4)(2) through the silver and acetyl oxygen (Ag-O = 2.534 (4) Angstrom) linkage between two waterwheel-like Ag6Cu2 units. All of the complexes show intense luminescence in the solid states and in fluid solutions. The microsecond scale of lifetimes in the solid state at 298 K reveals that the emission is phosphorescent in nature. The emissive state in compounds 1-5 is likely derived from a (LMCT)-L-3 (CdropCC(6)H(4)R-4 --> Ag4Cu2 or Ag6Cu2) transition, mixed with a metal cluster-centered (d --> s) excited state. The lowest lying excited state in compounds 6 and 7 containing electron-deficient 4-nitrophenylacetylide and 4-acetylphenylacetylide, respectively, however, is likely dominated by an intraligand (3)[pi --> pi*] character.