This paper shows the potentiality of capillary electrophoresis (CE) coupled to mass spectrometry (MS) for the analysis of heterocyclic aromatic amines obtaining good results in terms of sensitivity and precision. These compounds have a special interest since they can be carcinogenic for humans. The optimization of a CE-MS method was performed and the best conditions were obtained using a 16 mM formic acid/ammonium formate solution at pH 4.5 with 60% methanol as running electrolyte. For CE-MS coupling, a sheath liquid methanol/20 mM formic acid (75/25) solution at a flow rate of 3 muL/min and hydrodynamic injection of methanol mixtures for 10 s were used. Detection limits ranging from 18 ng/g to 360 ng/g and precisions up to 1.4% and 12% for migration time and concentration, respectively, were obtained. In order to improve sensitivity, field-amplified sample injection was applied as an in-line pre-concentration method. Methanol/5 mM formic acid (50/50) as a sample solvent, 3 s hydrodynamic injection (0.5 psi) of a methanol plug, and 25 s of electrokinetic injection (10 kV) of the sample were found to be the optimum conditions. Detection limits up to 25 times lower and similar precisions than those reported for hydrodynamic injection were obtained.