A new cyanogenic glucoside, isolated from pods of Acacia sieberiana var. woodii, was shown to be (2R)-2- (β-d-glucopyranosyloxy)-3-hydroxy-3-methylbutanenitrile by spectroscopic and chemical methods. The absolute configuration of this glucoside was correlated with that of proacacipetalin by oxymercuration of the latter, followed by borohydride reduction of the product.