Transmetalation of the beta-diketiminate salt [M]- [(Me)nacnac(Ph)] (M+ = Na or K; (M)(e)nacnac(Ph-) = {PhNC(CH3)}(2)CH-) with UI3(THF)(4) resulted in the formation of the homoleptic, octahedral complex [U((M)(e)nacnac(Ph))(3)] (1). Green colored 1 was fully characterized by a solid-state X-ray diffraction analysis and a combination of UV/vis/NIR, NMR, and EPR spectroscopic studies as well as solid-state SQUID magnetization studies and density functional theory calculations. Electrochemical studies of 1 revealed this species to possess two anodic waves for the U(III/IV) and U(IV/V) redox couples, with the former being chemically accessible. Using mild oxidants, such as [CoCp2][PF6] or [FeCp2][Al{OC(CF3)(3)}(4)], yields the discrete salts [1][A] (A = PF6-, Al{OC(CF3)(3)}(4)(-)), whereas the anion exchange of [1][PF6] with NaBPh4 yields [1][BPh4].