The reaction of (PuO2)-Pu-242 with HF and LiF under hydrothermal conditions results in the formation of Li4PuF8 and LiPuF5. These compounds were structurally characterized using single-crystal X-ray diffraction, and UV-vis-near-IR absorption spectroscopy was employed to confirm the oxidation state of the plutonium in the compounds as 4+. The structure of Li4PuF8 consists of [PuF8](4-) anions that adopt a bicapped trigonalprismatic geometry with approximate C-2, symmetry. These molecules are bridged by Li+ cations. In contrast, LiPuF5 forms a dense three-dimensional network constructed from [PuF9](5-)units that are bridged by F- anions. The Pu4+ cations are found within tricapped trigonal prisms. Extensive theoretical analysis of the electronic and bonding interactions is included with a comparison between the results active -space self-consistent-field at different levels of theory, quantum theory of atoms in molecules, interacting quantum atom, natural localized molecular orbital, and Wiberg bond order analyses. Covalent interactions in these compounds are examined, and intramolecular trends in covalent and electrostatic interactions are discussed.