A method using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) for the determination of the fatty acid composition of vegetable oils is described and illustrated with the analysis of palm kernel oil, palm oil, olive oil, canola oil, soybean oil, vernonia oil, and castor oil. Solutions of the saponified oils, mixed with the matrix, meso-tetrakis(pentafluorophenyl)porphyrin, provided reproducible MALDI-TOF spectra in which the ions were dominated by sodiated sodium carboxylates [RCOONa Na]. Thus, palm kernel oil was found to contain capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid. Palm oil had a fatty acid profile including palmitic, linoleic, oleic, and stearic. The relative percentages of the fatty acids in olive oil were palmitoleic (1.2 0.5), palmitic (10.9 0.8), linoleic (0.6 0.1), linoleic (16.5 0.8), and oleic (70.5 1.2). For soybean oil, the relative percentages were: palmitoleic (0.4 0.4), palmitic (6.0 1.3), linolenic (14.5 1.8), linoleic (50.1 4.0), oleic (26.1 1.2), and stearic (2.2 0.7). This method was also applied to the analysis of two commercial soap formulations. The first soap gave a fatty acid profile that included: lauric (19.4% 0.8), myristic (9.6% 0.5), palmitoleic (1.9% 0.3), palmitic (16.3% 0.9), linoleic (5.6% 0.4), oleic (37.1% 0.8), and stearic (10.1% 0.7) and that of the second soap was: lauric (9.3% 0.3), myristic (3.8% 0.5), palmitoleic (3.1% 0.8), palmitic (19.4% 0.8), linoleic (4.9% 0.7), oleic (49.5% 1.1), and stearic (10.0% 0.9). The MALDI-TOFMS method described in this communication is simpler and less time-consuming than the established transesterification method that is coupled with analysis by gas chromatography/mass spectrometry (GC/MS). The new method could be used routinely to determine the qualitative fatty acid composition of vegetable oils, and, when fully validated by comparison with standard analytical methodologies, should provide a relatively fast quantitative measurement of fatty acid mixtures and/or soap formulations that contain saturated and unsaturated hydrocarbon moieties.