The aim of this study was to determine the changes in the pentane concentration of expiratory gas as well as the relationship between this pentane concentration and hepatic oxidative stress during rabbit hepatic ischemia/reperfusion using solid-phase microextraction (SPME) and gas chromatography-mass spectrometry (GC/MS). 45 white male rabbits with body weights between 2.5 and 3.0 kg were randomly assigned to the following three groups: the 10 min ischemia group (group S); the 20 min ischemia group (group M); or the 30 min ischemia group (group L). Expiratory gases were collected prior to ischemia (T0) and for 1, 10, 20, 30, 60 and 120 min (T1-T6) following reperfusion. Pentane concentrations were determined using SPME and GC/MS. In addition, arterial blood samples were collected, and serum aminotransferase (AST) and malondialdehyde (MDA) concentrations were measured. In the three groups, the pentane concentrations of the expiratory gases at points T1 and T2 were significantly increased (P < 0.05) compared with those at point T0, and the serum AST and MDA concentrations at points T5 and T6 were also significantly increased (P < 0.05) compared with those at point T0. Therefore, the use of SPME in combination with GC/MS represents an improved anesthesia system that can be used to continuously measure the concentration of pentane in expiratory gases, which can reflect the degree of oxidative stress during hepatic ischemia/reperfusion.