Two new vernonioside K (1) and vernonioside L (2) and four known Δ 7,9(11) stigmastane-type steroidal saponins-vernonioside B2 (3), vernoniacum B (4), vernonioside B1 (5), and vernoamyoside A (6)were isolated from the leaves of Vernonia amygdalina. Their structures were determined by comprehensive spectroscopic analysis with one-dimensional nuclear magnetic resonance, twodimensional nuclear magnetic resonance, and high-resolution mass spectrometry. All isolated compounds (1-6) were evaluated to determine their inhibitory effects on α-glucosidase and xanthine oxidase. Among them, two new compounds 1 and 2 showed significant inhibition of α-glucosidase with IC 50 values of 78.56 ± 7.28 and 14.74 ± 1.57 (μM), respectively, comparable with acarbose as a positive control (127.53 ± 1.73 μM); none of these compounds inhibited xanthine oxidase activity. Compounds 1 and 2 are promising candidates for the development of antidiabetic agents from natural sources.