In a continuation of phytochemical studies on the underground organs of Liriope spicata var. prolifera, four new steroidal glycosides, lirioproliosides A-D, along with two known compounds, 25(S)-ruscogenin 1-O-[a-L-rhamnopyranosyl(1→2)[fl-D-xylopyranosyl(1→3)]-fl-D-fucopyranoside and ophiopogonin A, were identified. The structures of lirioproliosides A-D were established by a combination of spectroscopic and chemical methods as 25(S)-ruscogenin 1-O-[a-L-rhamnopyranosyl(1→2)][fl-D-xylopyranosyl(1→3)]-fl-D-fucopyranoside-3-O-a-L-rhamnopyranoside, 25(S)-ruscogenin 1-O-[3-O-acetyl-a-L-rhamnopyranosyl(1→2)]-fl-D-fucopyranoside, 25(S)-ruscogenin (1-O-[2-O-acetyl-a-L-rhamnopyranosyl(1→3)]-fl-D-fucopyranoside and ruscogenin (1-O-[2-Oacetyl-β-L-rhamnopyranosyl(1→2)]-fl-D-fucopyranoside, respectively. Among these steroidal glycosides, ophiopogonin A and lirioprolioside B, and lirioproliosides C and D, were isolated as epimeric pairs. Copyright