A method was established for the simultaneous determination of volatile organic compounds(VOCs)in surface water and drinking water by gas chromatography-triple quadrupole tandem mass spectrometry(GC-MS/MS)with head space-solid phase microextraction(HS-SPME).The performance of the five fibers was tested in univariate mode whereas the other variables affecting the efficiency of SPME analysis were optimized by factorial design and central composite design.The optimal SPME extraction conditions were as follows：75 μm of carboxen/polydimethylsiloxane fiber,5 mL of sample volume,40 min of extraction time,40 ℃ of extraction temperature,300 ℃ of desorption temperature,and 15.0% of NaCl.The analytes were determined by GC-MS/MS in selected reaction monitoring(SRM)mode,and the VOCs were quantified by internal standard method.Results showed that there were good linear relationships for 55 VOCs in the ranges of 0.04-0.4 μg/L,0.4-4.0 μg/L and 4.0-100 μg/L,respectively,with correlation coefficients(r2)all larger than 0.99.The limits of detection(LODs) and limits of quantification(LOQs)were in the range of 0.03-80 ng/L and 0.1-300 ng/L,respectively.Recoveries at three spiked levels of 0.2,2.0 and 40 μg/L ranged from 77.3% to 124% with relative standard deviations(RSDs,n=6) renged from 1.3%to 17%.The developed method was applied in the determination of VOCs in surface water and drinking water,in which 37 VOCs and 25 VOCs were detected,respectively.The method is accurate,reliable,simple,rapid and sensitive,and is suitable for the simultaneous detection of VOCs in surface water and drinking water.