The coordination chemistry of plutonium remains relatively unexplored. Thus, the fundamental coordination chemistry of plutonium is being studied using simple multi-dentate ligands with the intention that the information gleaned from these studies may be used in the future to develop plutonium-specific sequestering agents. Towards this goal, hard Lewis-base donors are used as model ligands. Maltol, an inexpensive natural product used in the commercial food industry, is an ideal ligand because it is an all-oxygen bidentate donor, has a rigid structure, and is of small enough size to impose little steric strain, allowing the coordination preferences of plutonium to be the deciding geometric factor. Additionally, maltol is the synthetic precursor of 3,4-HOPO, a siderophore-inspired bidentate moiety tested by us previously as a possible sequestering agent for plutonium under acidic conditions. As comparisons to the plutonium structure, Ce(IV) complexes of the same and related ligands were examined as well. Cerium(IV) complexes serve as good models for plutonium(IV) structures because Ce(IV) has the same ionic radius as Pu(IV) (0.94 {angstrom}). Plutonium(IV) maltol crystals were grown out of a methanol/water solution by slow evaporation to afford red crystals that were evaluated at the Advanced Light Source at Lawrence Berkeley National Laboratory using single crystal …