Two methods based on headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography–ion trap mass spectrometry (GC-IT/MS) were proposed for the analysis of volatile organic compounds (VOCs) in cork material used in the production of cork stoppers. The effect of various factors affecting the extraction efficiency was carried out by means of a 24 full factorial design. The first method allowed the extraction of 17 terpenes by using a divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber (50/30 μm). The optimal conditions were achieved when cork extract (5 mL) added with 2.3 g of NaCl was extracted during 35 min at 55 °C. The second method allowed the identification of 41 carbonyl compounds after in-solution (5 mL) derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA, 2.3 mg/mL), followed by an incubation period of 6 min at 52 °C and extraction during 36 min at the same temperature, using a PDMS/DVB (50/30 μm) fiber. Both methods are simple, solvent free and fast. These methods were applied to the analysis of different cork raw material showing significant differences in the amounts of volatile compounds analyzed. Alcanfor and α-terpineol were the terpenes compounds present at highest amounts, and within carbonyl compounds analyzed, some samples presented a high level of butanal, octanal, nonanal, and glyoxal.