Solid-state magic angle spinning (MAS)³¹P NMR spectra of [Ag(PPh₃)₂]NO₃1, [Ag{P(CH₂CH₂CN)₃}₂]NO₃2 and [Ag{P(C₆H₄Me-m)₃}₂]NO₃3 have been obtained. In addition, the crystal structures for 2 and 3 have been determined. The results from the high-resolution NMR study are consistent with the known structure of 1 and the structures of 2 and 3. In each case the ³¹P NMR spectra exhibit resolved splittings arising from ¹⁰⁷Ag and ¹⁰⁹Ag with ¹J(¹⁰⁹Ag³¹P) values of 524, 564 and 517 Hz for 1, 2 and 3, respectively. In 1 the two phosphorus nuclei are crystallographically non-equivalent, thus analysis of the ³¹P NMR spectrum indicates two chemically shifted phosphorus nuclei, δ_A 9.50 and δ_B 7.67, with ²J(³¹P_A³¹P_B)= 125 Hz. The two phosphorus nuclei of 2 are crystallographically and magnetically equivalent in the solid state as evident from the cross polarization/MAS ³¹P NMR spectrum, δ–9.56. Crystals of 2 are trigonal, space group Rca= 12.204(2), c= 26.418(5)Å, Z= 6. The Ag and P atoms are located on a, three-fold rotation axis with Ag at the centre of inversion. The Ag–P bond distance is 2.383(1)Å. The conformation of the cyanoethylphosphine ligands in 2 is analogous to the ribs of an umbrella in which the silver atom is encapsulated by the six cyano groups with an Ag ⋯ N separation of 3.439(2)Å. The two phosphorus nuclei in 3 are crystallographically equivalent but magnetically non-equivalent since the molecule sits on a two-fold axis but lacks a centre of inversion. As a consequence of this symmetry the two phosphorus nuclei have identical chemical shifts, δ 11.2; however, ²J(³¹P³¹P) can be determined from slow MAS experiments. For 3 the space group is orthorhombic Aba2, a= 15.142(1), b= 24.917(2), c= 10.2536(7)Å, Z= 4. The two phosphorus atoms are related by a crystallographically imposed two-fold axis. The nitrate group is chelated symmetrically to the Ag atom.