A convenient and efficient vicinal oxyalkynylation/aminoalkynylation of internal unactivated alkenes is achieved by means of a Cu-catalyzed radical cascade reaction of unsaturated ketoximes with ethynylbenziodoxolone (EBX) reagents. This protocol enables the synthesis of structurally valuable isoxazolines or cyclic nitrones and the introduction of an important alkyne group in a single operation. The reaction is characterized by a broad substrate scope for both unsaturated ketoximes and alkynylation reagents and a low catalyst loading.