Using liquor fermented grains as study object,the enzyme activities of amylase,glucoamylase,protease,cellulase,pectinase and lipase,and the content of esters including total esters,ethyl acetate,ethyl butyrate,ethyl caproate and ethyl lactate were detected during fermentation of liquor fermented grains. The correlation between average enzyme activities and esters production was studied by correlation analysis and principal component analysis.The result of correlation analysis showed that different enzymes had different correlation coefficient with esters production. Two principal components of 6 kinds of enzymes were obtained through principal component analysis,which represented two actions of enzymes. Based on the correlation between principal components and esters production,the effects of enzymes on the esters production were studied.