Headspace solid-phase microextraction (HS-SPME) combined with gas chromatography-mass spectrometry (GC-MS) was used to analyze the medium high temperature Daqu in Gujing Gongjiu, and a total of 108 volatile compounds were identified. By examining the β values of the compounds under different sample amounts, multiple headspace solid-phase microextraction (MHS-SPME) was applied to quantify the aldehydes and ketones, phenols, nitrogen, furans, lactones, terpenes at the 35 and 50 mg samples, and a total of 46 compounds were quantified. The recoveries of the method ranged from 76.83%-133.11%, the limits of detection (LOD) were lower than 103.818 ppb, and the relative standard deviation (RSD%) were less than 21.34%, which showed the method had good sensitivity and repeatability. The experimental results showed that MHS-SPME could be applied to the quantitative analysis of these 46 compounds in Daqu. The contents of measured compounds ranged from 3645.79?442.43 ng/g (3-methyl-2(5H)-furanone) to 6.32?1.03 ng/g (3-ethylbenzaldehyde). This method provided a new idea for quantifying the volatile components in Daqu, and the results also provided data support for the enterprise to improve the Daqu quality evaluation system.