The invention provides a detection method for simultaneously measuring residual toluene 2,4-diisocyanate (2,4-TDI), toluene 2,6-diisocyanate (2,6-TDI) and diphenylmethane diisocyanate (MDI) in the product by using precolumn derivatization-gas chromatography-mass spectrography. The method comprises the following specific steps: performing ultrasonic extraction on a sample, performing rotary evaporation and concentration on the extracting solution, reacting in an acidic aqueous solution, neutralizing with an alkali liquor, extracting by using an organic solvent, performing organic phase derivatization, removing excessive derivatization reagents with a buffer solution, taking the organic phase as a to-be-measured solution after solution separation, measuring and confirming by using a gas chromatography-mass spectrometer, carrying out a blank experiment, quantifying by using an external standard method, measuring the target compound in the sample solution, and the like. According to the method, the measurement parameters and test steps of the gas chromatography-mass spectrography are reasonably selected, the content of 2,4-TDI, 2,6-TDI and MDI in leather, artificial leather and textiles can be simultaneously measured by adopting selective ion scanning detection and external standard method quantification, and the results are simultaneously obtained by virtue of one-step pretreatment. The method has the characteristics of high precision, high interference resistance and low detection limit.