An atom-economical intermolecular iron-catalyzed oxyamination of alkenes is described. The insertion of the oxygenated and nitrogenated moieties from the hydroxylamine substrate was observed with full regio-and chemoselectivity for terminal alkenes in good yields. HFIP as a solvent appeared to have a synergistic effect with the iron catalyst to promote the formation of the oxyaminated products. Preliminary mechanistic studies suggest a pathway going through an aziridination reaction followed by the in situ ring opening.