Oat, as a unique nutritional crop, is a new attempt for Huangjiu fermentation. In order to further explore the higher alcohols, microbial community structure and the correlations in oat Huangjiu, and study the characteristics of oat Huangjiu, the changes of higher alcohols during fermentation of oat Huangjiu were quantitatively analyzed by headspace solid phase micro-extraction and gas chromatography-mass spectrometry. And the alteration of microbial community structure during fermentation of oat Huangjiu was detected by high-throughput sequencing. The correlation between higher alcohols and microorganisms was predicted using statistical principles. Eighteen kinds of higher alcohols such as β-phenylethyl alcohol and 3-methyl-1-butanol were detected in oat Huangjiu. Firmicutes and Ascomycota were the highest relative abundant of bacterium and fungal on phylum level, respectively. Lactococcus and Saccharomyces were the highest relative abundant of bacterium and fungal on genus level, respectively. A total of 869 correlations were established between higher alcohols and microorganisms. Correlation analysis revealed that 297 genera might be involved in the metabolism of higher alcohols. Fermenting Huangjiu with oat not only increased the variety and raw material source of Huangjiu, but also improved the nutritional value of Huangjiu. In addition, the correlation analysis between higher alcohols and microorganism predicted the biological mechanism of quality characteristics of oat Huangjiu.