Abstract: A novel method has been developed for the determination of captan in water samples by solid phase micro-extraction(SPME) coupled with gas chromatography-mass spectrometry (GC-MS/MS). Some important parameters affecting the extraction efficiency of SPME were studied and optimized. Under optimum conditions, the results showed that the linear range for the determination was 0.10~5.00 mg/L, and the correlation coefficient r² was greater than 0.99. The spiked recovery test was performed on farm irrigation water samples, and the low, medium and high spiked concentrations were determined. The average recoveries were 75.7%, 79.1%, and 83.1%, respectively, with the relative standard deviation(RSD) between 2.0% and 3.4%. The limit of detection(LOD) was 7.98 μg/L. The captan residues in water samples were successfully analyzed by the proposed method with satisfactory results.