An ambient ionization tandem mass spectrometric approach was developed to rapidly screen multiresidue pesticides on fruits and vegetables without sample preparation and chromatographic separation. The residual pesticides on fruits and vegetables were collected by sweeping a metallic probe across the sample surface for 2 cm. The analytes collected on the probe were desorbed and ionized in a thermal desorption electrospray ionization (TD-ESI) source, after which analyte ions were detected by a triple quadruple mass analyzer (QqQ) operated in multiple reaction monitoring (MRM) mode. With this TD-ESI/MS/MS approach, 308 pesticides were monitored, where a mixture containing 15 pesticide standards was successfully identified to demonstrate the capability of this approach to screen trace multiresidue pesticides. The approach had reasonable detection limits (<50 ppb) and reproducibility (RSD: 8.43%, n = 9) from the analysis of a benthiazole standard solution. Real samples including a tomato and bell pepper were analyzed using this TD-ESI/MS/MS approach. After TD-ESI/MS/MS analysis, the organic solvent extracts from the same samples were subjected to TD-ESI/MS/MS, gas chromatography mass spectrometry (GC-MS), and liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis for validation.