Oxygenation is af undamental transformation in synthesis.H erein, we describe the selective late-stage oxygenation of sulfur-containing complex molecules with groundstate oxygen under ambient conditions.T he high oxidation potential of the active uranyl cation (UO 2 2+ )e nabled the efficient synthesis of sulfones.T he ligand-to-metal charge transfer process (LMCT) from O2ptoU5f within the O=U=O group,w hich generates aU V center and an oxygen radical, is assumed to be affected by the solvent and additives,and can be tuned to promote selective sulfoxidation. This tunable strategy enabled the batch synthesis of 32 pharmaceuticals and analogues by late-stage oxygenation in an atom-and step-efficient manner.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.