Reaction of (tpyC 6 H 4 C≡CAu) n {tpyC 6 H 4 C≡CH = 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine) with diphosphane ligands Ph 2 P(CH 2 ) x PPh 2 (x = 2 dppe, 3 dppp, 4 dppb, 5 dpppen, 6 dpph) in CH 2 Cl 2 afforded the corresponding dual luminescent binuclear gold(I) complexes [(tpyC b H 4 C≡CAu) 2 -(μ-dppe)] (1), [(tpyC 6 H 4 C≡CAu) 2 (μ-dppp)] (2), [(tpyC 6 H 4 C≡ CAu) 2 (μ-dppb)] (3), [(tpyC 6 H 4 C≡CAu) 2 (μ-dpppen)] (4), [(tpyC 6 H 4 C≡CAu) 2 (μ-dpph)] (5). Crystal structural analysis of complexes 1·2CH 2 Cl 2 and 2·2CH 2 Cl 2 show that the terpyridine moieties are free of coordination in these gold(I)-acetylide-phosphane complexes. Spectrophotometric titration between complex 1 and [Eu(tta) 3 ] (Htta = 2-thenoyltrifluoroacetone) or [Yb(hfac) 3 (H 2 O) 2 ] (Hhfac = hexafluoroacetylacetone) gave a 2:1 ratio between Ln(β-diketonate) 3 (Ln = Eu, Yb) units and the complex 1 moiety, indicating the formation of Au 2 Ln 2 complexes. Both the luminescence titrations and the luminescence quantum yields of Au 2 Ln 2 (Ln = Eu, Yb) solutions show that the energy transfer occurs efficiently from the binuclear gold(I) antennas 1-5 to Eu III and Yb III centers, and all complexes 1-5 are good energy donors for sensitization of visible and NIR luminescence of Eu III and Yb III ions.