Abstract Two-, three- and four-coordinate silver(I) complexes, AgX (X = CN −, PF 6 - , and SbF 6 - ), with triphenyl phosphine, tricyclohexyl phosphine, diphenylcyclohexyl phosphine, and dicyclohexylphenyl phosphine have been synthesised and characterised by single crystal X-ray diffraction, elemental analysis, infrared spectroscopy, and 13C and 31P NMR spectroscopy. From the reaction of a metal salt to phosphine ligand ratio of 1:1 the various compounds crystallize as 1:2, 1:3, and 1:4 compounds [Ag(PPh 2Cy) 3(CN)]·5H 2O ( 1), [Ag(PCy 3) 2]·PF 6 ( 2), [Ag(PPh 3) 4)]·SbF 6·CHCl 3 ( 3), [Ag(PCy 3) 2]·SbF 6 ( 4), [Ag(PPh 2Cy) 2(C 3H 6O)]·SbF 6 ( 5), and [Ag(PPhCy 2) 2]·SbF 6.CHCl 3 ( 6) monomers, with a wide variety of geometries around the central silver(I) atom. Compounds 1 and 3 have slightly distorted tetrahedral geometry around the silver(I) atom. The compounds 2, 4, and 6 show linear geometry around the metal centre, while compound 5 has a distorted trigonal planar geometry. The elemental analysis and NMR spectroscopic results are consistent with the single crystal structural analyses.