A derivatization method for the analysis of 12 heterocyclic aromatic amines (HAs) in food, by gas chromatography-electron impact mass spectrometry, was developed. The amines are derivatized in a one-step reaction with N-methyl-N-(tert.-butyldimethylsilyl)trifluoroacetamide. The derivatives are characterized by easy-to-interpret mass spectra due to the prominent ion [M-57]+ by loss of a tert.-butyldimethylsilyl group, allowing quantification in the selected-ion monitoring mode at the picogram level. The effect of temperature, time, and reagents on the formation of the derivatives was monitored in detail. Quality parameters were evaluated in the optimum working conditions. This derivatization method is not applicable to the pyridoimidazoles Glu-P-1 and Glu-P-2 and to the beta-carboline harman due to incompletely derivatization. The instability of the imidazolquinoline and imidazoquinoxaline derivatives, requiring their injection on the same working day, is a further drawback. This simple, rapid and accurate derivatization procedure is suitable for routine analysis, as illustrated by the analysis of some common foods.