A new, fast, sensitive, and solventless extraction technique was developed in order to analyze beer carbonyl compounds. The method was based on solid-phase microextraction with on-fiber derivatization. A derivatization agent, O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBOA), was absorbed onto a divinyl benzene/poly(dimethylsiloxane) 65-microm fiber and exposed to the headspace of a vial with a beer sample. Carbonyl compounds selectively reacted with PFBOA, and the oximes formed were desorbed into a gas chromatograph injection port and quantified by mass spectrometry. This method provided very high reproducibility and linearity. When it was used for the analysis of aged beers, nine aldehydes were detected: 2-methylpropanal, 2-methylbutanal, 3-methylbutanal, pentanal, hexanal, furfural, methional, phenylacetaldehyde, and (E)-2-nonenal.