In neutral chemical compounds, the highest known oxidation state of all elements in the Periodic Table is +VIII. While PuO4 is viewed as an exotic Pu(+VIII) complex, we have shown here that no stable electronic homologue of octavalent RuO4 and OsO4 exists for PuO4, even though Pu has the same number of eight valence electrons as Ru and Os. Using quantum chemical approaches at the levels of quasi-relativistic DFT, MP2, CCSD(T), and CASPT2, we find the ground state of PuO4 as a quintet C-5(2v)-(PuO2)+(O-2)(-) complex with the leading valence configuration of an (f(3))plutonyl(V) unit, loosely coupled to a superoxido (pi(*3))O-2- ligand. This stable isomer is likely detectable as a transient species, while the previously suggested planar D D-1(4h)-Pu(VIII)O-4 isomer is only metastable. Through electronic structure analyses, the bonding and the oxidation states are explained and rationalized. We have predicted the characteristics of the electronic and vibrational spectra to assist future experimental identification of (PuO2)(+)(O-2())- by IR, UV-vis, and ionization spectroscopy.