Due to the globally existed and economically motivated adulteration including mislabeling and/or blending, fast wine characterization is important in wine industry. Herein, we developed an electrostatic spray ionization-mass spectrometry (ESTASI-MS)-based method to distinguish wines. Wine samples were directly analyzed by ESTASI-MS without any pretreatment. Microdroplets of wine were deposited on a plastic plate for analysis. The collection of each mass spectrometric datum can be accomplished in 1-2 min without any need of pretreatment to the sample, followed by principle component analysis to discriminate wines with different labels and vintages. Long-term storage of wine was simulated and characterized by utilizing the method. High-performance liquid chromatography-MS was further applied to identify the distinctive compounds in wines to indicate their difference. We found that the method can offer a strategy for quick wine analysis, which is of practical value in wine industry for wine classification and aging control.