The formula of five grains including sorghum, wheat, corn, rice and sticky rice is the particular feature for Wuliangye when compared with other Chinese liquors. In this study, the five grains powder was distilled for two times by water and the distillates were collected separately. The aroma extraction dilution analysis (AEDA) was applied to determine the odor-active compounds in two distillates. The results showed that 2-methylbutanal, hexanal, (E)-2-heptenal, benzaneacetaldehyde, guaiacol, p-cresol, m-cresol, ethyl hexanoate, dimethyl trisulfide and β-damascenone were the most important odor-active compounds (flavor dilution factor (FD)≥81) in 1^st distillation, and 2-methypropanal, (E)-2-heptenal, dimethyl trisulfide and guaiacol (FD≥81) were the most important odor-active compounds in the 2^nd distillation. The FD values of aldehydes (hexanal, (Z)-2-nonenal), aromatic compounds (benzaldehyde, benzeneacetaldehyde, acetophenone, 4-methylguaiacol, p-cresol and m-cresol), and ethyl hexanoate in 1^stdistillation were higher than that in 2^nd distillation. The FD factors of guaiacol, 4-ethylphenol, 2,3-butanedione and hexanol in the 2^nd distillation were higher than that in the 1^st distillation. This study compared the difference of odor-active compounds between the 1^st and 2^nd distillation of five grains powder and it provided an important database for future researches.