A core-excited sulfur state with a lifetime almost one order of magnitude longer than in molecular 2p core-hole states is selectively produced by ultrafast dissociation of S 2p → σ* excited OCS. Clear evidence for this is provided by strong atomic peaks (20% of the total intensity) in x-ray fluorescence but very weak ones (2%) in the corresponding resonant Auger spectrum. Corroborating the assignment of the spectra, ab initio calculations explain the enhanced lifetime: the Auger decay of the produced 3D3 (2p53p5) sulfur state is strongly decreased as it contradicts a newly derived propensity rule of the L2,3MM Auger decay.