In this study we demonstrate that electrospray-assisted laser desorption ionization (ELDI) mass spectrometry (MS) can be used to rapidly characterize major chemical components on the surfaces of different solids under ambient conditions. The major chemical components in (a) dried milks with different fat contents, (b) different color-regions of a painting, (c) the thin coating on a compact disc, (d) drug tablets, and (e) porcine brain tissue were rapidly characterized as protonated molecules [M+H](+) or sodiated molecules [M+Na](+) by ELDI-MS with minimum sample pretreatment. The ionized ions of synthetic polymer and dye standards were detected directly from dried sample solutions using either positive or negative ion mode. Further structural information for the FD&C Red dye was obtained through tandem mass spectrometric (MS/MS) analysis using an ion trap mass analyzer attached to the ELDI source.