Compounds of composition [BiPh(Hsal)2] (1) and [BiPh(Hsal4Me)2] (2) were prepared by the reactions of triphenylbismuth with 2-hydroxybenzoic acid (H2sal) or 4-methyl-2-hydroxybenzoic acid (H2sal4Me) in a 1:2 ratio. The reactions of 1 and 2 with bidentate nitrogen donor ligands 1,10-phenantroline (phen) and 2,2-bipyridine (bipy) led to the isolation of the corresponding adducts [BiPh(Hsal)2(phen)] (3), [BiPh(Hsal)2(bipy)] (4), [BiPh(Hsal4Me)2(phen)] (5), and [BiPh(Hsal4Me)2(bipy)] (6). Crystallographic analyses of the adducts showed the solids to have monomeric structures with six-coordinate Bi(III). One salicylato ligand is coordinated in a monodentate fashion and the other in a bidentate, chelating manner. The phenol oxygen atoms remain uncoordinated in both cases. The coordination geometry around Bi(III) in 3, 4, 5·Me2CO, 6·DMF can be described as distorted pentagonal pyramidal with an apical C atom, while the free space trans to the ipso carbon atom of the phenyl group is believed to accommodate a stereochemically active pair of electrons. The 1H data demonstrate that the salicylate ligands are fluxional in solution. It was shown that under different reaction conditions a number of bismuth(III) monomeric, dimeric and oligomeric complexes are produced, attesting a rich chemistry in this system.