A gas chromatography-tandem mass spectrometry (GC-MS/MS) was established for the determination of azocyclotin, cyhexatin and fenbutatin oxide residues in fruits and vegetables. Ethyl bromide magnesium in ether solution and sodium tetraethylborate were used as the derivatization reagents for azocyclotin, cyhexatin and fenbutatin oxide are reported in this paper. Samples of fruits and vegetables were extracted with hexane, and then a cleanup step using florisil SPE cartridge was applied. The purified extract was derived by ethyl magnesium bromide and sodium tetraethylborate, and then quantified by external standard method in multiple reactions monitoring mode(MRM). Under the optimized conditions, the target concentrations and peak areas were linearly correlated in the range of 0.01-2.00 mg/kg, and the correlation coefficients are greater than 0.99. Recovery studies were carried out on spiked matrices (the representative sample of cabbage, eggplant, potato, citrus and apple) with azocyclotin, cyhexatin and fenbutatin oxide at spiking levels of 0.01、0.02、0.05 mg/kg. The mean recoveries were 76.2%-92.0%, with relative standard deviations less than 8.5%. The response for the derivatives of azocyclotin and cyhexatin by these two derivatization reagents were close, but the response for the derivatives of fenbutatin oxide by solution of sodium tetraethylborate in water was about 1.69 times of ethyl magnesium bromide in ether solution. The response for the derivatives of fenbutatin oxide by the solution of sodium tetraethylborate in water was 1.5-2.3 times of ethyl magnesium bromide in ether solution. Organotin compounds were derived by sodium tetraethylborate in water solution was more efficient, simple and stable to meet the daily needs of laboratory testing.