The reactions of phenylaminobis(phosphonite), PhN{P(OC6H40Me-P)(2))}(2) (1) (PNP), with [AuCl(SMe2)] in appropriate ratios, afford the bi- and mononuclear complexes, [(AuCl)(2)(U-PNP)] (2) and [(AuCl)(PNP)](2) (3) in good yield. Treatment of 2 with 2 equiv of AgX (X = OTf or ClO4) followed by the addition of 1 or 2,2'-bipyridine affords [Au-2(mu-PNP)(2)](OTf)(2) (4) and [Au-2(C10H8N2)(2)(mu-PNP)](ClO4)(2) (5), respectively. Similarly, the macrocycles [Au-4(C4H4N2)(2)(mu-PNP)(2)](ClO4)(4) (6), [Au-4(C10H8N2)(2)(mu-PNP)(2)](ClO4)(4) (7), and [Au-6(C3H3N3)(2)(mu-PNP)(3)](ClO4)(6) (8) are obtained by treating 2 with pyrazine, 4,4'-bipyridine, or 1,3,5-triazine in the presence of AgClO4. The reaction of 1 with AgOTf in a 1:2 molar ratio produces [Ag-2(mu-OTf)(2)(mu-PNP)) (9). The displacement of triflate ions in 9 by 1 leads to a disubstituted derivative, [Ag-2(mu-PNP)(3)](OTf)(2) (10). The equimolar reaction of 1 with AgClO4 in THF affords [Ag-2(C4H80)(2)(mu-PNP)(2)](ClO4)(2) (11). Treatment of 1 with AgClO4 followed by the addition of 2,2'-bipyridine affords a discrete binuclear complex, [Ag-2(C10H8N2)(2)(mu-PNP)](ClO4)(2) (12), whereas similar reactions with 4,4'-bipyridine or pyrazine produce one-dimensional zigzag Ag' coordination polymers, [Ag-2(C10H8N2)(mu-ClO4)(ClO4)(mu-PNP)](n) (13) and [Ag-2(C4H4N2)(mu-ClO4)(ClO4)(mu-PNP)](n) (14) in good yield. The nature of metal-metal interactions in compounds 2, 4, 5, and 12 was analyzed theoretically by performing HF and CC calculations. The structures of the complexes 2, 4, 5, 7, 9, 12, and 14 are confirmed by single crystal X-ray diffraction studies.