To resolve the chromatographic column capacity of gas chromatography-mass spectrometry（GC-MS）,a GC-MS method with supercritical fluid chromatography（SFC） was developed for the determination of carbonyl compounds in mainstream cigarette smoke.The total particulate matter in mainstream cigarette smoke was collected with a Cambridge filter pad,and the carbonyl compounds were extracted with a supercritical fluid extractor,then the extract was separated and divided into 3 fractions by SFC method,and each fraction was analyzed by GC-MS.The results showed that the overlapping chromatographic peaks were avoided,and the chromatographic column capacity of GC-MS was improved.Therefore,the kinds of aldehydes and ketones aromatic components in mainstream cigarette smoke determined by the developed method were far more than that without SFC separation.Only 29 kinds of aldehydes and ketones compounds,including 7 kinds of aldehydes and 22 kinds of ketones,were identified without SFC separation,while 57 kinds of aldehydes and ketones compounds,including 13 kinds of aldehydes and 44 kinds of ketones,were determined using the developed method.There were great differences in the species and contents of aldehydes and ketones in mainstream smoke of three cigarettes.Each cigarette contained different specific aldehydes and ketones in mainstream cigarette smoke.This study provided a new method for the determination of aldehydes and ketones in cigarette mainstream smoke.