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A new colorimetric sensor array was developed for the discrimination of 12 high-alcoholic Chinese base liquors from Luzhou Co., Ltd., and 15 commercial Chinese liquor of different brands as well as flavor types. Seventeen volatile compounds within four chemical groups were determined as markers in the base liquor by GC-MS analysis and factor analysis method (FAM). A specialized colorimetric sensor array composed of 20 sensitive dots was fabricated accordingly to obtain sensitive interaction with different types of volatile markers. Discrimination of the liquor samples was subsequently performed using chemometric and statistical methods, including principal component analysis (PCA) and hierarchical clustering analysis (HCA). The results suggested that facile identification of either base liquors with high-alcoholic volume or commercial liquors of the same flavor types could be achieved by analysis of the color change profiles. The response of the sensor improved significantly in comparison with those that rely on nonspecific interactions, and no misclassification was observed for both liquor samples using two chemometric methods. Besides, it was also found that the discrimination is closely related to the characteristic flavor compounds (esters, aldehydes, and acids) and alcoholic strength in liquors, and its performance was even comparable with that of GC-MS.