OBJECTIVE: To establish the method for simultaneous determination of 6 residual organic solvents in Xingnaojing injection, such as methanol, ethanol, isopropanol, n-butanol, ethyl acetate and acetonitrile. METHODS: Headspace GC method was adopted. The determination was performed on DB-624 capillary column by temperature programming with the injector temperature of 200 ℃; flame ionization detector was adopted with the temperature of 250 ℃; carrier gas was nitrogen with flow rate of 25 mL/min and split ratio of 35 ∶ 1; headspace sampling size was 1 mL, and heating temperature of headspace sampling was 80 ℃; equilibrium time was 15 min. RESULTS: The linear ranges of methanol, ethanol, isopropanol, n-butanol, ethyl acetate and acetonitrile were 15.00-240.00 μg/mL(r=0.999 9),25.00-400.00 μg/mL(r=0.999 9),25.00-400.00 μg/mL(r=0.999 9), 25.00-399.99 μg/mL(r=0.999 9),25.00-399.99 μg/mL(r=0.999 8) and 5.00-80.00 μg/mL(r=0.999 9). The LOQ were 5.98, 3.94, 2.05, 2.13, 1.39, 1.24 μg/mL, and the LOD were 2.01, 2.11, 1.18, 1.56, 1.15, 0.01 μg/mL, respectively. RSDs of precision tests were all less than 2.0%,stability and repetitive tests only ethyl acetate was detected,RSD<2.0%; the recoveries were 93.59%-99.02%(RSD=2.62%,n=6), 92.42%-98.40%(RSD=2.43%,n=6),94.81%-104.64%(RSD=3.47%,n=6),94.56%-106.73%(RSD=4.21%,n=6), 97.04%-106.33%(RSD=3.50%,n=6) and 98.40%-107.97% (RSD=3.37%,n=6). CONCLUSIONS: The method is specific, rapid, simple and accurate, and can be used for simultaneous determination of 6 residual organic solvents in Xingnaojing injection.