New naturally occurring spirostane saponin (25S)-5β-spirostan-3β-yl-3-O-β-D-xylopyranosyl(1 → 3)-O-β-D-xylopyranosyl(1 → 4)-β-D-galactopyranoside (6) and biflavonoid glycoside myricetin-3-O-rhamnoside (C7-O-C7) myricetin-3-O-rhamnoside (4) along with a series of known compounds erythrodiol (1), 3β-O-trans-p-coumaroyl-erythrodiol (2), quercetin-3-O-α-L-rhamnoside (3) and myricetin-3-O-α-L-rhamnoside (5) were separated from the leaves of Acacia saligna (Labill.), H.L. Wendl. Compounds 1 and 2 were separated for the first time from genus Acacia. The structures of compounds 1-6 were established on the basis of extensive 1D and 2D NMR spectroscopic techniques in combination with EI-MS and HR-ESI-MS. These compounds were screened for their antioxidant and cytotoxic activities against HEPG2 (liver cancer) cell line and significant results were obtained.