Abstract: A method was developed to analyze the volatile organic compounds (VOCs) in patchouli by combining comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS). Patchouli sample was pretreated with supercritical CO2 fluid extraction and molecular distillation,then the lighter distillates were detected by GC×GC-TOFMS. The Rxi-5sil MS was selected as the first dimension column and Rtx-200 as the second dimension column. TOFMS software combined with mass spectrum analysis was used for qualitative and quantitative analysis of compounds. The result showed that there were 323 constituents having matching degree above 750,including 67 ketones,52 alcohols,40 alkenes,37 acids,36 alkanes,34 ethers,17 aldehydes and 40 others. The abundance of those 323 constituents is 89.45%. In addition,there were 69 compounds with abundances above 0.1%,including 11 compounds with abundance above 0.1%. Pogostone (21.75%) and patchouli alcohol (18.93%) were the main constituents.