Trichloroaniline in the air was collected with 50% ethanol and separated with a column OV-17:OV-210 ECD as a detector. The best conditions of sampling and determining were selected through the orthogonal experimental design. The detectable limit was 0.01 mg/L. When the concentration of trichloroaniline in the air was 0.5-10 mg/L, the relative standard deviation (RSD) was 4.3%-3.7%. There was a linear relation within the range of 0.02-40 mg/L. The sampling efficiency was 99.1%-100%. The samples were stable for at least 15 days. It is proved that this method is accurate, fast, simple and sensitive. It is suitable for the determination of trichloroaniline in the air.