By employing silver salts with a weakly coordinating anion Ag[A] ([A]=[FAl{OC F } ], [Al{OC(CF ) } ]), two phosphaalkynes could be coordinated side-on to a bare silver(I) center to form the unprecedented homoleptic complexes [Ag(η -P≡CtBu) ][FAl{OC F } ] (1) and [Ag(η -P≡CtBu) ][Al{OC(CF ) } ] (2). DFT calculations show that the perpendicular arrangement in 1 is the minimum energy structure of the coordination of the two phosphaalkynes to a silver atom, whereas for 2 a unique square-planar coordination mode of the phosphaalkynes at Ag was found. Reactions with donor molecules yield the trigonally planar coordinated silver salts [((CH ) CO)Ag(η -P≡CtBu) ][FAl{OC F } ] (3) and [(C H ) Ag(η -P≡CtBu)][FAl{OC F } ] (4). All of the compounds were comprehensively characterized in solution and in the solid state.