A methodology for rapid determination of key "caramel aroma" compound (sotolon) in Chinese rice wine by liquid-liquid microextraction (LLME) combined with gas chromatography-mass spectrometry (GC-MS) was developed. The detective and quantitative limits of the method were 0.66 μg/L and 1.02 μg/L respectively, the recoveries varied from 80% and 120%, the intraday and inter-day precision were within 10%, which suggested that the method could meet the needs for rapid testing. The methodology was successfully applied to determine the content of sotolon in 24 typical rice wine samples from different regions, and the results showed that sotolon was a common aroma compound in rice wine with the concentration ranging from 42.05 to 244.34 μg/L. The odor threshold of sotolon (11 μg/L) in rice wine was determined for the first time. The aroma contribution of sotolon in rice wine was studied based on the odor activity value (OAV), and the results showed that the contents of sotolon in all the samples were higher than the odor threshold, and thus indicated that sotolon played an important role in the overall aroma of rice wine. In addition, the contents of sotolon in rice wine from Zhejiang and Shanghai regions were significantly higher than those from other areas, which further indicated that it is a potential compound for distinguishing rice wines from different regions.