Five cyanoglucosides have been isolated from extracts of the epidermal layer of barley and the structure of their trimethylsilyl derivatives have been elucidated spectroscopically (UV, NMR, MS). Three of these, namely 3-β-D-glucopyranosyloxy-3-methylbutyronitrile, 1-cyano-3-β-D-glucopyranosyloxy-2-methylpropene and 4-β-D-glucopyranosyloxy-3-hydroxy-3-hydroxymethyl-butyronitrile, are novel compounds.