Surgical procedures can induce traumatic stress responses, which are associated with postoperative complications. Therefore, a perioperative monitor is needed to identify patients with a higher degree of stress responses. We explored the relationship between breath volatile organic compounds (VOCs), a non-invasive method widely explored in disease diagnosis, and surgical traumatic stress. Exhaled breath and blood samples were collected from 105 patients under general anaesthesia at three time points: prior to incision (Pre-op), 2h after incision (Intra-op), and prior to extubation (End-op). Differential VOCs between these time points were screened. Blood metabolomics analysis, traumatic stress-related biomarkers detection, and correlation analysis between VOCs and stress biomarkers were performed. We found that both the abundance of VOCs and blood metabolites changed significantly between these time points. Norepinephrine, epinephrine and cortisol all increased significantly in Intra-op and then reduced significantly in End-op. Correlation analysis showed both Comp_6 and Comp_23 were negatively correlated with norepinephrine in group comparison between Intra-op and End-op, the same trend as that in group comparison between Pre-op and Intra-op. We conclude that surgical traumatic stress resulting from surgical procedures may change the exhaled breath VOC profile in perioperative patients, providing preliminary evidence for VOC use in future monitoring.