The utility of adding ion mobility (IM) to quadrupole time of flight mass spectrometry (IM-QTOF MS) for highly effective analysis of multiple pesticides in complex matrices was evaluated. Based on an in-house IM-MS database, the identification was performed through the match of the protonated ion ([M + H]+) and the CCS value. Moreover, the structural confirmation was achieved by using the accurate masses of [M + H]+ with its fragment ions, and the reference CCS value. The method did not require chromatographic separation and the analysis time of each measurement cycle is 1.6 min. The "cleaned" IM-MS spectra afforded by the drift time filtration improved the reliability of structural confirmation. As a result, the limit of detection (LOD) of 92% of test pesticides under the APCI mode and 58% of test pesticides under the ESI mode spiked in scallion was not more than 20 ng mL-1. In the analysis of practical samples, the identification of pyrimethanil was confirmed in celery, and benalaxyl and tebuconazole were identified as false positives in scallion. The time-saving, extended-scope and high-throughput method described in this work is capable of determining multiple pesticide residues in complex matrices with high sensitivity for monitoring applications.