AbstractThe four steroid sapogenins1, 2, 3, and4were obtained as solvolysis products of the enzymatic hydrolysis of a crude oligoglycoside fraction prepared from the aqueous extract of the starfishAsterina pectiniferaMüller et Troschel (Asterinidae). Two novel steroid oligoglycoside sulfates,5and6, were also obtained from the same crude glycoside fraction. On the basis of chemical and spectroscopic evidence, the structures of these sapogenins were determined as (3β,5α,6α)‐3,6‐dihydroxypregn‐9(11)‐en‐20‐one (asterone) (1), (3β,5α,6α,20S)‐3,6,20‐trihydroxycholest‐9(11)‐en‐23‐one (20S‐thornasterol A)1,3)(2), (3β,5α,6α,20R, 22R,23S,24S)‐22,23‐epoxy‐3,6,20‐trihydroxy‐24‐methylcholest‐9(11)‐ene (aglycone of regularoside A)4)(3), and (3β,5α,6α,20S,24ξ)‐24‐ethyl‐3,6,20‐trihydroxycholest‐9(11)‐en‐23‐one (4). The oligoglycosides were characterized as the 6‐O‐β‐D‐fucopyranosyl‐(1→2)‐β‐D‐glucopyranosyl‐(1→4)‐[β‐D‐quinovopyranosyl‐(1→2)]‐β‐D‐quinovopyranosyl‐(1→3)‐β‐D‐quinovopyranoside5of the 3‐O‐sodium sulfate of2and the 6‐O‐β‐D‐galactopyranosyl‐(1→4)‐[β‐D‐fucopyranosyl‐(1→2)]‐β‐D‐glucopyranosyl‐(1→4)‐[β‐D‐quinovopyranosyl‐(1→2)]‐β‐D‐xylopyranosyl‐(1→3)‐β‐D‐quinovopyranoside6of the 3‐O‐sod um sulfate of3. Compound3has not yet been isolated as aglycone, and compound4is a novel natural product. Moreover, the sugar moieties of compounds5