Herein, we describe a convenient and general method for the oxidation of olefins to ketones using either tris(dibenzoylmethanato)iron(III) [Fe(dbm)₃] or a combination of iron(II) chloride and neocuproine (2,9-dimethyl-1,10-phenanthroline) as catalysts and phenylsilane (PhSiH₃) as additive. All reactions proceed efficiently at room temperature using air as sole oxidant. This transformation has been applied to a variety of substrates, is operationally simple, proceeds under mild reaction conditions, and shows a high functional-group tolerance. The ketones are formed smoothly in up to 97 % yield and with 100 % regioselectivity, while the corresponding alcohols were observed as by-products. Labeling experiments showed that an incorporated hydrogen atom originates from the phenylsilane. The oxygen atom of the ketone as well as of the alcohol derives from the ambient atmosphere.