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Pigeonpea grains are important sources of vegetarian proteins. It is the paramount importance to check the pesticide residues due to their frequent use during production. The LC–MS/MS and GC–MS/MS analytical method was developed and validated for the simultaneous determination of 79 pesticide residues in pigeonpea. The LOD and LOQ of the analytical method were in the range of 0.53 to 3.97 and 1.60 to 10.05 µg kg⁻¹, respectively, with a correlation coefficient of more than 0.997. Average recoveries were in the range of 80 to 118.8%, with the RSD of less than 15%. Measurement uncertainty (U_x) for pesticides was in the range of 3.42 to 12.76 µg kg⁻¹ evaluated at 50 µg kg⁻¹. The method was applied to analyze the sample collected from the farmer’s field. This method could be useful for routine analysis of selected pesticide residue for monitoring purposes.