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Isoflavonoids possess a 3-phenylchroman skeleton and are the biologically active secondary metabolites of various plants that are used for different health promoting and restoring effects through a variety of mechanisms. Chromatographic separation of the <i>n</i>-hexane extract from the stems of <i>Placolobium vietnamense</i> led to the isolation of a new isoflavone derivative, placovinane (<b>1</b>), together with four known compounds (<b>2</b>–<b>5</b>). The structures of isolated compounds were identified from their spectroscopic data and by comparison with the literature. All isolated compounds were evaluated for their <i>α</i>-glucosidase inhibition. They all exhibited potent <i>α</i>-glucosidase inhibition with IC₅₀ values ranging from 11.0 to 87.3 µM, which was significantly less than the positive control acarbose (IC₅₀ 179 µM). The cytotoxicity of <b>1</b> was evaluated against KB, Hep G2, and MCF7 cell lines, and displayed weak cytotoxicity toward KB and Hep G2 cell lines, with the IC₅₀ values of 89.6 and 93.8 μM, respectively.