The structural elucidation of eleven new related polyoxypregnane glycosides, gymnepregosides G (1), H (2), I (3), J (4), K (5), L (6), M (7), N (8), O (9), P (10) and Q (11), from the roots of Gymnema alternifolium (Asclepiadaceae) was achieved by a detailed study of ¹H- and ¹³C-NMR spectral data chemical means. The results obtained for new compounds, 1-11, show that they are (20S)-pregn-6-ene-3β, 5α, 8β, 12β, 14β, 17β, 20-heptaol 3-O-glycosides, and all the sugars at C-3 are β(1→4)linked. Some of them possess benzoyl, (E)- and (Z)-cinnamoyl, and tigloyl residues as the ester linkages located at C- 12 and/or C-20 of the aglycone.