Chemical and spectroscopic evidence for the constitution and stereochemistry of veralkamine, a minor alkaloid from Veratrum album subsp. lobelianum (Bernh.) Suessenguth, has been given. In alteration of a former structural suggestion veralkamine is regarded as (22S:25S)-22,26-epimino-17β-methyl-18-nor-17-iso-cholesta-5,12-dien e-3β.16β-diol [(17S:22S:25S)-22,26-epimino-18(13→17)-abeo-cholesta-5m12-diene-3 β, 16β-diol,I] representing a novel structural type of steroidal alkaloids. © 1968.