A new triterpenoid saponin, designated macrophyllicinin [1], has been isolated from the MeOH extract of the whole plant of Primula macrophylla. Its structure was established by chemical and spectroscopic means as 3 beta-O-[alpha-L-rhamnopyranosyl-(-->2)-beta-D-glucopyranosyl-(-->2)- beta-D-galactopyranosyl-(-->2)-beta-D-glucuronopyranosyl]-6 beta,16 alpha-dihydroxyolean-12-en-28-acetate. The aglycone 2 of this saponin is also a new compound.