Systematic examinations were made on the alkaloids of Veratrum grandiflorum (MAXIM.) LOESENER FIL growing in Hokkaido. As the free bases, jervine (yield, 0.2%), veratramine, and rubijervine were isolated and identified. The so-called amorphous base was found to contain a few kinds of unknown ester-alkaloids, as evidenced by paper chromatography, and these were separated by chromatopile. The main alkaloid was obtained in 0.01% yield as a substance (Ea) of C₃₂H₄₇O₈N·H₂O, m.p. 235°(decomp.), [α]¹⁵ -10.9°(c=1.65, CHCl₃); UV λ_max^EtOH 217 mμ (log ε 3.00); IR λ_max^EtOH 5.82, 6.02 μ. Examination of the hydrolyzate of (Ea) showed it to be the zygadenine δ-lactone monoester of angelic acid.