The ability to selectively extract lanthanides is crucial in hydrometallurgy and the nuclear fuel cycle. The capabilities of 1-hydroxy-6-N-octylcarboxamido-2(1H)-pyridinone (octyl-HOPO) as an extractant for the separation of lanthanides and actinides were studied for the first time. Octyl-HOPO greatly outperformed the traditional ligand di-2-ethylhexyl phosphoric acid (DEHPA).