Three new triterpene glycosides, hebevinosides XII, XIII and XIV, were isolated besides five already known neurotoxic hebevinosides from acetone extract of the mycelium with primordia of a poisonous mushroom, Hebeloma vinosophyllum, and their structures were deduced to be 3β, 7β, 16β-trihydroxycucurbita-5, 24-diene-3-O-β-D-xylopy-ranoside-16-O-(4-O-acetyl)-β-D-glucopyranoside, 3β, 7β, 16β-trihydroxycucurbita-5, 24-diene-3-O-(3, 4-di-O-acetyl)-β-D-xylopyranoside-16-O-(4, 6-di-O-acetyl)-β-D-glucopyranoside and 3β, 7β, 16β-trihydroxycucurbita-5, 24-diene-3-O-(3, 4-di-O-acetyl)-β-D-xylopyranoside-16-O-(6-O-acytyl)-β-D-glucopyranoside, respectively.Productivity of the eight hebevinosides was studied at three growth stages of the organism; mycelium (stage I), mycelium with primordia (stage II) and mycelium with fruit-bodies (stage III). The ratio of production of total hebevinosides at stages I : II : III was approximately 6 : 4 : 25. Production of hebevinosides VII, XIV, XIII, VIII and XII having the acetyl groups at O-4 in the glucosyl and/or O-3 in the xylosyl moieties, which are comparatively labile, decreased, and that of hebevinosides III and II having the acetyl groups at O-6 in the glucosyl and/or O-4 in the xylosyl moieties, which are relatively stable, increased in the time course from stage I to stage III. On the other hand, production of hebevinoside VI having no acetyl group was independent of the growth stages. Production of ergostane-type sterols seemed to be activated for the first time at stage III in the organism.