The structure of verazine, C27H43NO, a new minor alkaloid from Veratrum album subsp. lobelianum (Bernh.) Suessenguth has been established. The two tetrahydroverazines A and B, obtained by catalytic hydrogenation, have been shown to be identical with (22S:25S)- and (22R:25S)-22,26-imino-5α-cholestan-3β-ol (IV and V), formerly synthesized by ourselves from 3β--acetoxy-pregn-5-en-20-one. On the basis of these results as well as NMR, IR, UV, CD, ORD and mass spectroscopic investigations verazine is regarded as (25S)-22,26-imino-cholesta-5,22(N)-dien-3β-ol (I) representing a novel structural type of Veratrum alkaloid of biogenetic interest. © 1967.