In order to explore comfort difference after drinking different flavor Baijiu, blood alcohol concentration (BAC) was measured by breath alcohol detector, and determination method was optimized. The area under the BAC curve after drinking was used to construct an evaluation model to determine comfort index after drinking different flavor Baijiu, and the correlation between comfort index and main flavor components was studied by Pearson coefficient. The results showed that different dietary patterns and drinking intervals had significant impacts on BAC (P<0.05), while drinking speed had no significant impact on BAC (P>0.05). The relative standard deviation of BAC measured using the optimized method was less than 5%. There was no significant difference between after drinking comfort index of the same Baijiu measured by different volunteers and the mean value of 89.3±0.8 (P>0.05), indicating that the evaluation model had good reproducibility. The comfort index after drinking 11 kinds of Baijiu among the 12 flavor Baijiu determined by evaluation model were significantly different from that of super grade alcohol group (P<0.05). The correlation analysis showed that comfort index after drinking Baijiu was significantly negatively correlated with content of acetaldehyde, acetal, ethyl formate, ethyl acetate, ethyl isovalerate, and isoamyl alcohol (P<0.01), and negatively correlated with the content of isovaleraldehyde, ethyl butyrate, n-propanol, n-amyl alcohol, and acetic acid (P<0.05). Among them, isoamyl alcohol had the greatest negative effect on comfort index after drinking Baijiu. The logarithm of the total amount of flavor components negatively correlated with comfort index after drinking was used for polynomial fitting, and the regression equation y=-5.453+66.605x-7.137x² (R²=0.849, P<0.01) was obtained. There was no significant difference between comfort index predicted by the regression equation and the measured value (P>0.05). The research offered certain reference value for evaluation of comfort of solid Baijiu after drinking.