Abstract: The headspace sampling (HS) method is a simple, environmentally friendly method. The measurement of 59 kinds of volatile organic compounds(VOCs) in environmental water using HS coupled gas chromatography/mass spectrometry (GC/MS) was discussed. Under the optimal headspace sampling conditions, a detector gain of 1.00 kV, a sample salinity of 40%, an equilibrium temperature of 80℃, an equilibrium time of 10 min, an equilibrium pressure of 0.103 4 MPa, a pressure equilibration time of 45 s, a loop equilibration time of 20 s, a loop inject time of 3 min were get up, and the obtained detection limits were 0.06~7.6 μg/L, with r>0.998. The obtained average recovery ratios were 60%~110% (n=6) in spiked samples from drinking source and sewage plants, with a RSD of 0.33%~22% (n=6). The HS-GC/MS method with automatic water pretreatment can be applied to the simultaneous measurement of 59 VOCs in water samples with high efficiency.