Abstract: Headspace-solid phase microextraction(HS-SPME),combined with direct-gas chromatography-olfaction(D-GC-O)method,was used in the study on volatile flavor components of Luzhou-flavor baijiu. Compared with the static headspace(SHS)method,the optimum extraction conditions were examined from the aspects of aroma component detection and overall odor impression,and the key aroma components of Luzhou-flavor baijiu were analyzed. The results showed that the optimal extraction method was HS-SPME:75 μm CAR/PDMS extraction fiber,extraction temperature 45℃,equilibrium time 15 min,extraction time 40 min,salt addition 3 g. 77 aroma components in Luzhou-flavor baijiu were quantitatively analyzed. 46 kinds of odorants were identified by GC-O-MS,including 22 esters,7 alcohols,4 acids,7 aromatic compounds,5 furans,aldehydes and ketones,1 sulfur compound. 18 key aroma components in Luzhou-flavor baijiu were determined by aroma intensity values and odor activity value(OAV)analysis,which mainly showed floral,fruity,sweet,acidic,grassy,alcoholic,cellar and so on. In this study,the overall odor impression was used as the judgement basis for determining the optimal extraction conditions. Sensory data was further provided to ensure the credibility of the optimal conditions on the basis of the detection of flavor compounds. The identified key aroma components were able to well represent the characteristics of Luzhou-flavor baijiu.