1,2-Dehydropyrrolizidine alkaloids are common toxic metabolites isolated from plants within the Boraginaceae, in particular from the genera Heliotropium and Echium. Previous studies have deduced the structures of these often potent bioactives based upon mass spectrometric evidence, but these identifications have not established conclusive connectivity and configurational data. Herein, we describe the isolation and full structural characterization of echivulgarine, occurring in the pollen of Echium vulgare and correct the structure previously ascribed to the compound, using a comprehensive combination of both experimental and calculated nuclear magnetic resonance and electronic circular dichroism spectroscopic data.