Pyrazines are important compounds in soy sauce aroma type Baijiu (SSAB). In this work, a total of 16 pyrazines were analyzed using ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC–MS/MS) in SSAB. The quantitative results showed that 2,3,5,6-tetramethylpyrazine, 2,6-dimethylpyrazine and 2,3,5-trimethylpyrazine were the three most concentrated pyrazines. The highest odor activity value (OAV) was determined for 2-ethyl-3,5-dimethylpyrazine. Quantitative analysis combined with descriptive sensory analysis revealed that sub-threshold pyrazines (2,3-dimethylpyrazine, 2,3-diethylpyrazine, 2,3-diethyl-5-methylpyrazine and 2-acetyl-3-methylpyrazine) are significantly correlated with the roasted aroma in SSAB. Our study focused on the impact of sub-threshold pyrazines on the perception of roasted aroma in SSAB. The effect of the sub-threshold pyrazines was detected by the addition of various pyrazines in SSAB samples, despite their sub-threshold concentrations. Furthermore, the presence of sub-threshold pyrazines in dilute alcohol solution resulted in a significant reduction in the odor thresholds of supra-threshold pyrazines. Sensory investigation indicated that pyrazines have a synergistic effect on the perception of roasted aroma. The results highlighted the contribution of some pyrazines to the roasted aroma in SSAB despite their sub-threshold concentrations.