In this work, we proposed an electrochemical method for directly recording the profiles of the electroactive compounds in Chinese liquor. We selected samples from 11 brands with four flavor types to investigate the feasibility of the proposed method. Owing to the different raw materials in the fermentation process, different brands of Chinese liquor contain different small molecules that could contribute to differences during an electrochemical scan. Principal component analysis (PCA) and cluster analysis were conducted. The results indicate that the electrochemical profiles of these brands can be distinguished using their voltammetric data. We also selected two distinct peaks corresponding to the electro-oxidation of the electroactive compounds for authentication. The 11 brands were successfully differentiated using a flow chart. In addition, the flow chart has been successfully applied to actual sample analysis.