Selected triacylglycerols (TAGs) were directly analyzed on a standard stainless steel target plate by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Sodium and potassium ion adducts of TAGs were produced, and the thermal desorption/ionization mechanism was invoked to rationalize the experimental observations. The method permits a simple and fast qualitative analysis of TAGs. Advantages of this approach relative to matrix-assisted laser desorption/ ionization (MALDI) are simpler sample preparation, lack of need to use a matrix with consequent absence of matrix interference peaks in the spectra, and potential improvements in shot-to-shot reproducibility due to the absence of the crystallization step resulting in a more homogenously deposited sample. The procedure was successfully applied to the determination of TAGs in whole oils, yielding very fast TAG fingerprints.