Adducts of triphenyl phosphine, triphenyl arsine, and triphenyl stibine with silver(l) bromate have been synthesized and characterized both in solution (H-1 and ESI MS spectroscopy) and in the solid state (IR, single-crystal X-ray structure analysis). The triphenyl phosphine complexes have been also investigated by P-31{H-1} solution and P-31 cross-polarization magic-angle-spinning (CPMAS) NMR spectroscopy. The topology of the structures in the solid state was found to depend on the nature of EPh3 and on the stoichiometric ratio AgBrO Ph-3. In AgBrO/PPh3 (1:1)(4) (1) and AgBrO4/PPh3 (1:2) (2), the bromate is in the unfamiliar and hitherto structurally uncharacterized role of coordinating ligand, the complex having a mononuclear form in 2 and a less familiar tetrameric form in 1. In AgBrO3AsPh3 (1:4).CH3OH (7) and AgBrO3/SbPh3 (1:4) . C2H5OH (11), the cations are the familiar homoleptic [Ag(EPh3)(4)](+) array with the bromate role simply that of counterion. The AgBrO3/AsPh3 (1:2)(2).0.7"H2O" derivative (6) is binuclear L2Ag(mu-BrO3)(2)AgL2 with a four-membered ring core (L = AsPh3).