Laser desorption ionization time-of-flight mass spectrometry (LDI-TOF MS) was used to characterize olive and sunflower oils before and after thermally assisted oxidation in order to develop a rapid fingerprinting method for oil that contains unchanged and oxidized components. No matrix was used to assist laser desorption, and simplified mass spectra were obtained in the mass range of interest (m/z 500-1000), where triacyl- and diacylglycerol ions were observed. Sample preparation was reduced to dissolving oil in chloroform saturated with NaCl. Sodiated triacylglycerols (TAGs), their epoxy/hydroxy and hydroperoxy derivatives, as well as TAGs with shortened chain fatty acids (beta-scission products) were clearly observed in the spectra. LDI-TOF MS rapidly provides semiquantitative information about the oxidation level of edible oil, and thus represents a very useful quality control tool.