Abstract: Currently, organophosphorus pesticides are widely used in agriculture, industry and other fields. However, they have also caused serious environmental pollution issues. Therefore, it is of valuable significance to establish a fast, sensitive and accurate detection method for organophosphorus pesticides in water. A Solid-Phase Micro-Extraction (SPME) probe with an organic/inoganic composite coating was prepared by a simple sol-gel method. A low-cost and convenient SPME device was developed by refitting a gas chromatography syringe. A new method has been established for simultaneous determination phorate, disulfoton, methyl parathion,parathion and isocarbophos in environmental water samples by SPME-Gas Chromatography (SPME-GC-MS). The detection limits were between 1.2 μg/L and 3.9 μg/L. The relative standard deviations (RSD, n=6) were between 0.8% and 7.4%. The recoveries were between 93 and 112% for natural samples with an internal standard. The established method was qualified for fast determination of organophosphorus in environmental water sample with a good use value and potential. The organic/inorganic hybrid probe could be recycled up to 100 times, its extraction effect is better than that of commerical polyacrylate and polydimethylsiloxane (PDMS) probes. The SPME device could also be reused after probe replacement.