AbstractBACKGROUNDBeer is a popular alcoholic malt beverage resulting from fermentation of the aqueous extract of malted barley with hops. The aroma of brewing barley impacts the flavor of beer indirectly, because some flavor compounds or their precursors in beer come from the barley. The objectives of this research were to study volatile profiles and to characterize odor‐active compounds of brewing barley in order to determine the variability of the aroma composition among different brewing barley cultivars.RESULTSForty‐one volatiles comprising aldehydes, ketones, alcohols, organic acids, aromatic compounds and furans were identified using solid phase microextraction combined with gas chromatography/mass spectrometry, among which aldehydes, alcohols and ketones were quantitatively in greatest abundance. Quantitative measurements performed by means of solvent extraction and calculation of odor activity values revealed that acetaldehyde, 2‐methylpropanal, 3‐methylbutanal, 2‐methylbutanal, hexanal, heptanal, octanal, nonanal, 3‐methyl‐1‐butanol, cyclopentanol, 2,3‐butanedione, 2,3‐pentanedione, 2‐heptanone, acetic acid, ethyl acetate, 2‐pentylfuran and benzeneacetaldehyde, whose concentrations exceeded their odor thresholds, could be considered as odor‐active compounds of brewing barley.CONCLUSIONPrincipal component analysis was employed to evaluate the differences among cultivars. The results demonstrated that the volatile profile based on the concentrations of aroma compounds enabled good differentiation of most barley cultivars. © 2014 Society of Chemical Industry