Denitrative Hydroxylation of Unactivated Nitroarenes**

Abstract A one‐step method for the conversion of nitroarenes into phenols under operationally simple, transition‐metal‐free conditions is described. This denitrative functionalization protocol provides a concise and economical alternative to conventional three‐step synthetic sequences. Experimental and computational studies suggest that nitroarenes may be substituted by an electron‐catalysed radical‐nucleophilic substitution (S RN 1) chain mechanism.