The reaction of Ph3BiCl2 with alkali salts of isonicotinic and nicotinic acids afforded Ph3Bi[O(O)CC5H4N-4]2 (1) and Ph3Bi[O(O)CC5H4N-3]2 (2), respectively, which were characterized by multinuclear NMR spectroscopy in solution, mass spectrometry and IR spectroscopy in the solid state. Their molecular structures were established by single-crystal X-ray diffraction. For both 1 and 2 the molecules contain a trigonal bipyramidal C3BiO2 core, with the phenyl groups in equatorial positions. The potential use of 1 and 2 as ditopic organometalloligands was investigated. The reaction of 1 or 2 with Me3SnCl (1 : 2 molar ratio) resulted in carboxylato ligand exchange and the formation of Me3Sn[O(O)CC5H4N-4] (3) and Me3Sn[O(O)CC5H4N-3] (4) besides Ph3BiCl2. The crystals of both 3 and 4 contain 1-D coordination polymers built through intermolecular N → Sn interactions. The treatment of Ni[S2P(OiPr)2]2 with 1 and 2, respectively, resulted, in addition to di(carboxylato)nickel(ii) derivatives, in isolation of Ph3Bi and the disulphane [(iPrO)2P(S)S]2. New coordination polymers were obtained by reacting 1 and 2 with various silver(i) salts: [Ag{Ph3Bi[O(O)CC5H4N-4]2}(OTf)] (5), [Ag{Ph3Bi[O(O)CC5H4N-3]2}(OTf)]·CH2Cl2 (6·CH2Cl2), [Ag{Ph3Bi[O(O)CC5H4N-4]2}](SbF6)·2THF (7·2THF), [Ag{Ph3Bi[O(O)CC5H4N-3]2}](SbF6)·CH2Cl2 (8·CH2Cl2) and [Ag{Ph3Bi[O(O)CC5H4N-3]2}(NO3)]·CH2Cl2 (9·CH2Cl2). The crystal structures of 5 and 6 can be described as 1-D chains linked by triflate bridges in pairs of chains and 2-D networks, respectively. Compound 7 features a 2-D grid-like topology of the network, with tecton 1 acting as a tridentate ligand through both nitrogen and one oxygen atoms. The linker 2 molecules adopt either cis (compound 6) or trans (compounds 8 and 9) conformation. Complexes 8 and 9 are 1-D chain polymers exhibiting zig-zag and wavy motifs, respectively. The dimensionality of the structures is extended by the presence of supramolecular interactions (ππ, AgAg, AgO).