Aliphatic thiolates were efficiently converted into the corresponding sulfenates by smooth oxidation with trans-(±)-2-tert-butyl-3-phenyloxaziridine at room temperature (fiveexamples). Subsequent electrophilic quench with benzylbromide led to sulfoxides (S-alkylation) in good to moderateyields. Application of the protocol to an aromatic substratewas also successful. This work represents the first valuableexample of the use of this poorly active oxidizing agent insynthetic organic chemistry without the need for activatingconditions.