Abstract: To study the chemical constituents of Dioscorea zingiberensis Wright, the EtOH extract of fresh rhizomes of D.zingiberensis was concentrated and partitioned further to produce petroleum ether-, ethylacetate-, n-butanol- and water-soluble fractions. The water-soluble fraction was subjected to column chromatography on macro resin AB-8, and the final products were obtained by repeated reversed-phase ODS and MCI gel CHP 20P column chromatography. Structures of compounds were elucidated by means of ¹H NMR, ¹³C NMR, ¹³⁵DEPT, HMQC, HMBC and TOCSY spectroscopic analyses. Five steroidal saponins were isolated, in which one new steroidal saponin was identified as (25R)-26-O-(β-D-glucopyranosyl)-furost-5-en-3β,22ξ,26-triol-4β-acetoxyl-3-O-β-D-glucopyranosyl-(1→3)-β-D-glucopyranosyl-(1→4)-［α-L-rhamnopyranosyl-(1→2)］-β-D-glucopyranoside (V). The compound V is a new compound, named as zingiberenin G. The compounds I, II and III were reported for the first time from D.zingiberensis Wright.