In order to probe the effect of solvent and substituents on the formation of bismuth carboxylates, triphenylbismuth (BiPh3) was treated with salicylic acid, 5-bromosalicylic acid, 3-methoxysalicylic acid, 5-nitrosalicylic acid, 3-methylanthranilic acid, 5-chloroanthranilic acid, and N-acetylanthranilic acid in a 1:2 ratio in a variety of solvents. The following compounds were isolated and structurally characterized: [PhBi(5-Br-2-OH-C6H3CO2)2(Me2CO)], 1; [PhBi(5-Br-2-OH-C6H3CO2)2(EtOH)]·(EtOH) (H2O), 2; [PhBi(5-O2N-2-OH-C6H3CO2)2(4,4′-bipy)]·EtOH (4,4′-bipy = 4,4’-bipyridine), 3; [PhBi(5-Cl-2-NH2-C6H3CO2)2], 4; [Ph2Bi2(3-MeO-2-OH-C6H3CO2)4(EtOH)], 5; [Ph2Bi2(3-MeO-2-OH-C6H3CO2)4(i-PrOH)], 6; [PhBi(2-MeC(O)NH–C6H3CO2)2]·EtOH, 7; [PhBi(3-MeO-2-OH-C6H3CO2)2]∞·PhCH3, 8; [PhBi(3-Me-2-NH2-C6H3CO2)2(2,2′-bipy)]·0.42MeCN; (2,2′-bipy = 2,2′-bipyridine), 9; cis-[PhBi(5-Br-2-OH-C6H3CO2)2]2, 10; trans-[PhBi(5-Br-2-OH-C6H3CO2))2]2·2MeCN, 11; [PhBi(5-Br-2-OH-C6H3CO2))2]2·2MeOH, 12, trans- [PhBi(2-OH-C6H4CO2)2]2, 13. Compounds 1 and 2 are monomeric possessing a coordinated solvent molecule in an equatorial coordination site of a pentagonal pyramidal bismuth(III) center. The same coordination geometry is found in 3 where two such units are tethered together via the 4,4’-bipyridine ligand. Compounds 5 and 6 form dimers in which one Bi atom attains a pentagonal pyramidal geometry via coordination of the solvent and the other via binding to the phenol group of a 3-methoxysalicylate ligand attached to the other Bi atom. Compounds 7 and 8 are polymeric. In 7, a coordination polymer is created by the donation of the acetyl oxygen atom of the [PhBi(2-MeC(O)NHC6H3CO2)2] unit to an adjacent [PhBi(2-MeC(O)NHC6H3CO2)2] center, while in 8 a similar situation arises but through the phenolic and methoxy oxygen atoms of a 3-methoxysalicylate ligand, giving rise to the first observed hexagonal pyramidal coordination complex of a bismuth carboxylate. In 9, one of the carboxylate ligands is bidentate while the other remains monodentate, displaying the same structural geometry as previously reported for [PhBi(2-MeO-C6H4CO2)2(2,2′-bipy)]·0.5EtOH and [PhBi(4-Me-2-OH-C6H3CO2)2(2,2′-bipy)]. Compounds 10–13 are dimeric structures arising from shared carboxylate oxygen atoms that bridge the two bismuth atoms.