We report the first transmission of solvent-coordinated dipositive plutonyl ion, (PuO22+)-O-VI, from solution to the gas phase by electrospray ionization (ESI) of plutonyl solutions in water/acetone and water/acetonitrile. ESI of plutonyl and uranyl solutions produced the isolable gas-phase complexes, [An(VI)O(2)(CH3COCH3)(4,5,6)](2+), [An(VI)O(2)(CH3CO-CH3)(3) (H2O)](2+), and [An(VI)O(2)(CH3CN)(4)](2+); additional complex compositions were observed for uranyl. In accord with relative actinyl stabilities, (UO22+)-O-VI > (PuO22+)-O-VI > (NpO22+)-O-VI, the yields of plutonyl complexes were about an order of magnitude less than those of uranyl, and dipositive neptunyl complexes were not observed. Collision-induced dissociation (CID) of the dipositive coordination complexes in a quadrupole ion trap produced doubly- and singly-charged fragment ions; the fragmentation products reveal differences in underlying chemistries of plutonyl and uranyl, including the lower stability of Pu(VI) as compared with U(VI). Particularly notable was the distinctive CID fragment ion, [Pu-IV(OH)(3)](+) from [(PuO2)-O-VI(CH3COCH3)(6)]2(+), where the plutonyl structure has been disrupted and the tetravalent plutonium hydroxide produced; this process was not observed for uranyl.