Volatile constituents in raw liquor and zaopei during fermentation and distillation were investigated by gas chromatography. Zaopei (steamed grains mixed with Daqu [FG1], stacking fermented grains [FG2], anaerobic fermented grains [FG3] and steamed grains [FG4]) presented changes in physicochemical properties. In all, 72 volatile compounds were identified in zaopei and raw liquor with similarity across 12 zaopei preparations. Principal component analysis and partial least squares discriminant analysis differentiated FG3 from other samples based on content of aroma compounds. FG3 had the highest level of aroma compounds, which increased from the fourth to sixth batches, and was characterised by the presence of 1, 2-propanediol, acetic acid and linoleic acid, while the others were portrayed by phenylpropionate, ethyl laurate and 4-ethyl guaiacol. The volatile compounds of raw liquor were dominated by ethyl acetate and ethyl lactate. Correlation analysis illustrated a lack of correlation of volatile compound content between the raw liquors and the zaopei distillation variants.