A series of tri- and tetranuclear phosphine complexes of d(10) metal ions supported by the polydentate ligands, bis(diphenylphosphinomethyl)phenylphosphine (PPP) and tris(diphenylphosphinomethyl)phosphine (PPPP), were synthesized. All the compounds under study, [AuM2(PPP)(2)](3+) (M = Au (1), Cu (2), Ag (3)), [M-4(PPPP)(2)](4+) (M = Ag (4), Au (5)), [AuAg3(PPPP)(2)](4+) (6), and [Au2Cu2(PPPP)(2)(NCMe)(4)](4+) (7), were characterized crystallographically. The trinuclear clusters 1-3 contain a linear metal core, while in the isostructural tetranuclear complexes 4-6 the metal framework has a plane star-shaped arrangement. Cluster 7 adopts a structural motif that involves a digold unit bridged by two arms of the PPPP phosphines and decorated two spatially separated Cu-I ions chelated by the remaining P donors. The NMR spectroscopic investigation in DMSO solution revealed the heterometallic clusters 2, 3, and 6 are stereochemically nonrigid and undergo reversible metal ions redistribution between several species, accompanied by their solvation-desolvation. The complexes 1-3 and 5-7 exhibit room temperature luminescence in the solid state (Phi(em) = 6-64%) in the spectral region from 450 to 563 nm. The phosphorescence observed originates from the triplet excited states, determined by the metal cluster-centered d(sigma*) -> p(sigma) transitions.