A headspace solid-phase microextraction (HS-SPME) method is proposed for analyzing the main volatile components from a sensory standpoint (furfural, oak lactones, eugenol, vanillin, and syringaldehyde) present in nontoasted and toasted oak wood of different origins. To maximize the yield of compounds extracted from wood chips and to obtain a good precision of the method, the most important variables affecting HS-SPME have been studied. The best results were obtained when the sample was heated at 70 degrees C and the headspace extracted for 40 min with a DVB/CAR/PDMS fiber, which gave the overall best recovery. The values for the repeatability ranged from 6.4 to 7.8%, and those for the reproducibility from 5.4 to 8.7%. The precision of the results obtained makes the proposed technique appropriate for its use in characterizing oak wood samples of different origins and in the selection of the most suitable oak wood to age wines and spirits, on the basis of the chemical composition of the wood samples.