This paper aims to establish a headspace (HS) gas chromatography-mass spectrometry (GC-MS) method for the detection of sevoflurane, desflurane, enflurane, isoflurane, halothane and hexafluoroisopropanol in biological samples. Blood samples (1.0 mL) and equivalent volume of deionized water were added into a 10 mL headspace vial, before the vial was sealed. The vial was extracted at 65 ºC for 5 minutes and then the headspace was analyzed by GC-MS (EI), with the data being acquired under full scan mode. Sevoflurane, desflurane, enflurane, isoflurane, halothane and hexafluoroisopropanol showed good linear relationship between peak area and concentration within the investigated concentration ranges, with their coefficients of determination(R²) being over 0.990 2. The lower limit of detection (LLOD) and limit of quantification (LOQ) for six analytes ranged 0.04－0.5 μg/mL and 0.06－1 μg/mL, respectively. Their average recoveries among 61.19%－90.39%. The precision (RSD) of intra-day and inter-day behaved satisfied between 1.62%－17.29% and 0.85%－17.91%. The method is of high speed, simplicity, efficiency and low interference for determination of sevoflurane, desflurane, enflurane, isoflurane, halothane and hexafluoroisopropanol.