The volatile oils in fresh red pine needles from Xiao Hinggan Mountains,were extracted by steam distillation,and then analyzed by comprehensive two dimensional gas chromatography-time of flight mass spectrometry（GC×GC-TOF MS）.The chromatographic separation conditions were optimized,and the best conditions were confirmed to be a modulation period of 6 s,a second dimensional column length of 3 m,and a temperature of 20 ℃ for the second dimensional column higher than that for the first dimensional column all the time.Under the optimal conditions,217 kinds of compounds were identified based the NIST library,and the quantitative calculation was carried out by area normalization method.Total of the compounds identified was four times more than that identified by one dimensional gas chromatography（1DGC）.124 terpenoids,including 48 monoterpenoids,64 sesquipenoids and 12 diterpenoids were identified from the volatile oils of fresh red pine needles,accounting for about 69% of all.And 33 ester compounds accounting for about 12% of all,6 organic acids,15 alcoholic compounds,15 aldehyde compounds,11 ketone compounds and 13 other compounds were also identified.Compaired with the one dimensional gas chromatography,two dimensional gas chromatography- time of flight mass spectrometry possesses higher resolution and sensitivity,and it shows a unique superiority in the analysis of complex natural products.