We have developed an efficient radical α-oxyamination reaction using chiral organocatalysts. The reaction can be carried out with inexpensive SET reagents, and a reasonably broad substrate scope has been established. Good to high enantioselectivity for the α-oxygenated products are obtained using 20 mol % of the catalyst. The methodology reported in this work adds to the repertoire of asymmetric radical reactions that can be conducted using organocatalysts.