Bi(III) ions are capable of reversible, multicomponent self assembly with suitable tris-coordinate ligands. The nature of the self-assembled structures observed are dependent on the ligand coordination geometry, ligand protonation state and Bi concentration. These assemblies can exploit the maximum number of coordination sites at the Bi vertices (nine), and the self-assembly process has been studied by 1D NMR, Diffusion NMR, ESI-MS and X-ray crystallographic analysis. V-shaped coordinating ligands reversibly form discrete M₂L₄, M₂L₃, and M₂L₂ complexes dependent on ligand/bismuth concentration, whereas a linear coordinating ligand forms a single discrete M₃L₃ assembly.