A series of lanthanum benzoate complexes have been prepared and structurally characterised as DMF or DMSO solvates. The structures of these complexes vary considerably as a function of the steric bulk of the ligands and the degree of solvation. With one exception, all of the complexes form coordination polymers. These experimental results are compared to reported data from the Cambridge Structural Database (CSD) in order to study the role of sterically bulky substituents in the structures of lanthanum benzoate complexes. Binding modes vary from the η1 coordination of a carboxylic acid co-ligand to carboxylate ligands adopting a bridging μ-η2 : η1 geometry. The nature of the bridging environment between adjacent lanthanum ions varies significantly in the structures and often several different environments exist within the same structure. Solvent effects are also observed, particularly in cases where the solvent is able to partake in intra- or intermolecular hydrogen bonding.