The synthesis and structural characterization of the first example of a uranyl(VI) complex possessing unsupported unidentate thiolate ligands, UO2(S-2,6-Cl2C6H3)(2)L-2 (2b, L = N,N-diisobutylisopropylamide), are reported. Isolation of 2b as a stable mononuclear complex is provided by the alkyl substituents of the organic amide ligands, which offer enhanced solubility, electron-releasing properties, and steric protection to help saturate the uranyl(VI) coordination sphere.