For the fist time, key volatile compounds in the headspace of aromatic water from ponkan has been analyzed using headspace solid -phase microextraction (HS -SPME) combined with gas chromatography -mass spectrometry (GC-MS). The effects of SPME fiber (PDMS/DVB 65 μm, CAR/PDMS 75 μm and DVB/CAR/PDMS 50/30 μm), adsorption temperature (30~50℃), adsorption time (5~30min) and sample volume (2~10 mL) were studied to develop HS-SPME condition for obtaining the highest extraction efficiency. For the headspace volatile extraction, the optimum conditions were: DVB/CAR/PDMS fiber, 8 ml of sample volume, adsorption at 40octanol, 6.2℃ for 20 min. The main volatile flavor compounds were: d-limonene, 40.85%; ethanol, 17.17%; a-terpineol, 15.61%; 1-0%; β-myrcene, 3.48%; 3-methyl-1-butanol, 3.01%; β-linalool, 2.93%; naphthalene, 2.88%; ethyl caprylate, 2.34%; α-pinene, 1.47%. Ten kinds of compounds accounted for 95.94% of total peak area. Relative standard deviation (RSD) for three replicate analyses was found to be less than 7.0% and confirmed the feasibility of the HS -SPME -GC/MS technique for headspace analysis of key volatile compounds in aromatic water from ponkan. ©, 2015, Chinese Institute of Food Science and Technology. All right reserved.