Upon reacting P4S3 with AgAl(hfip)4 and AgAl(pftb)4 [hfip = OC(H)(CF3)2; pftb = OC(CF3)3], the compds. Ag(P4S3)Al(hfip)4 (1) and Ag(P4S3)2+[Al(pftb)4]- (2) formed in CS2 or CS2/CH2Cl2 soln., resp. Compds. 1 and 2 were characterized by single-crystal x-ray structure detns., Raman and soln. NMR spectroscopy, and elemental analyses. One-dimensional chains of [Ag(P4S3)x]... (x = 1 (1); x = 2 (2)) formed in the solid state with P4S3 ligands that bridge through a 1,3-P,S, a 2,4-P,S, or a 3,4-P,P h1 coordination to the silver ions. Compd. 2 with the least basic anion contains the 1st homoleptic metal(P4S3) complex. Compds. 1 and 2 also include the long sought sulfur coordination of P4S3. Raman spectra of 1 and 2 were assigned from DFT calcns. of related species. The influence of the silver coordination on the geometry of the P4S3 cage is discussed, addnl. aided by DFT calcns. Consequences for the frequently obsd. degrdn. of the cage are suggested. An exptl. silver ion affinity scale based on the solid-state structures of several weak Lewis acid base adducts (L)AgAl(hfip)4 is given. The affinity of the ligand L to the silver ion increases according to P4 < CH2Cl2 < P4S3 < S8 < 1,2-C2H4Cl2 < toluene. [on SciFinder (R)]