Abstract: The content of ethanol in wine can affect its quality. Some edible alcohol contains small amounts of methanol, and its accumulation can cause serious health problems. Therefore, it is very important to test the contents of methanol and ethanol in alcohol products. In this paper, a rapid method for the determination of methanol and ethanol by ambient corona discharge ionization mass spectrometry was developed. The method is based on the interaction of water radical cation with methanol and ethanol, respectively. In the positive ion mode, the water dimer radical cation (H₂O)₂^+· (m/z 36) with ambient corona discharge ionization source was prepared by using ambient corona discharge ionization source, and it was introduced into the mass spectrometer with methanol or ethanol through a dual-channel low-energy corona discharge ionization device. The two reacted with each other to form the corresponding water radical cationic complex CH₃OH+H₂O^+· (m/z 50) and CH₃CH₂OH+H₂O^+· (m/z 64), which realized the direct and rapid qualitative and quantitative analysis of methyl alcohol and ethanol in different kinds of alcoholic beverages. The result showed that the limits of detection and the limits of quantification of methanol and ethanol were 0.011 and 0.004 mg/L, 0.038 and 0.014 mg/L, respectively. The correlation coefficients of the target ionic strength curves obtained by the interaction of different concentrations of standard methanol and ethanol with water free radical cation could reach to 0.990 4 and 0.991 1, respectively. By using this method, no methanol was detected in common alcoholic drinks, and the ethanol content in liquor was higher than beer. In the actual work, the method has good practicability through the experimental exploration and verification of different wines. This method does not require sample pretreatment, has the advantages of simple operation and fast analysis, and is especially suitable for the detection of aqueous system. This study has important guiding significance for the quantitative detection and analysis of methanol and ethanol in complex system, provides technical support for the detection of alcoholic beverages and food, and also provides an effective strategy for the quantitative detection of the content of small and medium molecular alcohols in actual samples.