An unprecedented triterpene alkaloid glycoside, designated cimicifugadine (1), with a pyridine ring incorporated to a cycloartane triterpenoid nucleus, was isolated from the roots of Cimicifuga foetida. Its structure was established on the basis of extensive spectroscopic measurements and chemical transformation with the absolute configuration at C-24 determined to be S by a modified Mosher method. It demonstrated a novel reactivity in mild acidic media whereby the cyclopropane ring is opened followed by the formation of two isomeric conjugated trienes.