A copper-catalyzed three-component reaction of alkenes, acetonitrile, and sodium azide afforded gamma-azido alkyl nitriles by formation of one C(sp3)-C(sp3) bond and one C(sp3)-N bond. The transformation allows concomitant introduction of two highly versatile groups (CN and N3) across the double bond. A sequence involving the coppermediated generation of a cyanomethyl radical and its subsequent addition to an alkene, and a C(sp3)-N bond formation accounted for the reaction outcome. The resulting g-azido alkyl nitrile can be easily converted into 1,4-diamines, g-amino nitriles, g-azido esters, and g-lactams of significant synthetic value.