Abstract: Under the optimized experiment conditions, aromatic amines reduced from various azo dyes in textiles were directly detected by electrospray ionization mass spectrometry (ESI-MS). Under the following experimental conditions: temperature of the heating capillary at 100℃, the flow rate of sheath gas at 25 arb units, the sample flow rate at 10 μL/min and 5 kV ESI voltage, the total ion current of signal was stable and of the highest intensity. Thus, 19 types of carcinogenic aromatic amines were detected and identified using ESI-MS/MS and characteristic ions of all the precursor ions tested were obtained. Based on ESI-MS/MS analytical technique, a new method for rapid detection of aromatic amines in textiles was established to inspect various practical samples such as cotton clothes, silk textiles and etc. with advantages of improved sensitivity, good specificity, high sample throughput and low detection limits at sub ng/L level.