The constituents of the roots and rhizoma of Veratrum maackii reg. (Liliaceae), which are used as a Chinese crude drug “Li-lu,” were examined and a new steroidal alkaloid named maackinine was isolated along with five known alkaloids, germanitrine, verazine, angeloylzygadenine, zygadenine, and verazinin. The structure of maackinine was determined by the use of two-dimensional nuclear magnetic resonance (2-D NMR) techniques (fl-decoupled 1-1—'H chemical shift correlation spectroscopy (COSY), 11-1—'11 COSY, →-→C COSY, and long-range JH-13C COSY spectra). Assignments of 1H- and 13C-NMR signals of these steroidal alkaloids were also performed. © 1989, The Pharmaceutical Society of Japan. All rights reserved.