Abstract: D-1-Naphthylamine as internal standard, four aromatic amines (1-naphthylamine, 2-naphthylamine, 3-aninobiphenyl, 4-aninobiphenyl) in cigarette mainstream smoke were analyzed by GC/MS, through hydrochloric acid ultrasound, methylene dichloride and n-hexane extraction, trimethylamine hydrochloride and pentafluoropropionic anhydride derivation, solid-phase extraction wash and purification process. The RSDs of four aromatic amines are less than 5%, and the recovery are 89.8%-106.0%. The limits of detection of four aromatic amines are 0.03-0.07 ng/cig. The method is accuracy, reproducibility and suits for analysis of four aromatic amines.