The qualitative and quantitative determination of 32 pesticide residues in surface water was established by gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS). In the experiment, 32 kinds of pesticide residues were extracted at one time by optimizing the pre-treatment; and multiple qualitative ions were selected to ensure the accuracy of the results by optimizing the mass spectrometry parameters of the target compound; the unstable effect of ionization efficiency was eliminated by introducing internal standard of heptachlor B; the interference of matrix effect on pesticide residue detection was avoided by preparing standard curve of matrix. The results showed that the linear range (10~600 μg/l) of the tested residues had good linear relationship: the linear coefficient was ≥0.995, the detection limit was 0.04~0.08 μg/L, the quantitative limit was 0.2 μg/L, and the recoveries were 73.9%~108.8%. The method had the advantages of simple pretreatment, high instrument sensitivity and good selectivity, suitable for daily quantitative analysis of pesticide residues in surface water.