<jats:title>Abstract</jats:title><jats:p>The extraction and the isolation of some alkaloids from the roots of an African plant (<jats:italic>Securidaca Longipedunculata Fres</jats:italic>) are reported. The structural characterization was performed by mass spectrometry. Alternative ionization methods (FAB and EI), collisionally‐induced decomposition experiments and accurate mass measurements revealed the presence of elymoclavine and dehydroelymoclavine and the presence of a new ergoline alkaloid.