Thermal desorption-electrospray ionization tandem mass spectrometry (TD-ESI/MS/MS) was used to characterize the residual pesticides that were collected from the surface of a grape with metallic sampling probes. Fungicides, insecticides, and miticides were detected, where results were validated by simple solvent extraction followed by gas chromatography tandem mass spectrometry and liquid chromatography tandem mass spectrometry analyses. To explore the distribution of pesticide residues on grape surfaces, 149 locations of a grape surface were collected and followed by TD-ESI/MS/MS analysis. The molecular cartography was then generated from analysis of residual pesticides on the grape surface in 3D.