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High performance liquid chromatography-coulometric electrochemical array detection (HPLC-ECD) could be used to detect with electrochemical active substances. Meanwhile, these substances are the sensory substances of Chinese spirits, particularly in sensory evaluation. A method using HPLC-ECD on Chinese spirits was established for the first time. Under the optimal chromatographic conditions, when using 8 channels, 102 characteristic peaks in Chinese spirits could be identified. All peaks were well separated with high stability and precision. The method was direct injection without pretreatment, and it did not need to qualitatively and quantitatively analyze the detected substances, which meant this method was simple, fast, low cost and high efficiency. Using this method, the Chinese spirits produced by traditional fermentation and the Chinese spirits produced by alcohol blending could be distinguished. A variety of active substances in these two kinds of Chinese spirits could be detected, the fingerprint information was rich, and there were obvious differences between the two kinds of Chinese spirits. Cluster analysis was also used for the detection of data processing, and it could achieve an accurate distinction between these two kinds of Chinese spirits. Furthermore, the method was used to analyze the liquor with different blending ratios, and the results were accurate. The liquor was divided into four groups accurately: the proportion was divided into 10%, 15%, 75% and 100%. All these data showed that this method was suitable for classification and determination of Chinese spirits.