In this study, a method of simultaneous determination of 19 kinds of polychlorinated biphenyls in aquatic products by gas chromatography-quadrupole time-of-flight mass spectroscopy was established. The samples were extracted by the use of dispersed high-speed homogenization technique with mixed solution of acetone and petroleum ether as extraction solvent, the extracting solution doubly purified by concentrated sulfuric acid and chromatographic column, eluted by n-hexane. The extracting solution was separated by GC capillary column(HP-5MS) with helium as a carrier gas at the flow rate of 1.5mL/min. The resultant separation was ionized by electron impact ion source. The data were collected by TOF/MS full scan mode. The qualitative analysis was performed using retention time and ion precise mass number, and the quantitative analysis was performed using the external standard method. The results showed that the calibration curves of 19 kinds of PCBs showed good linearities when the concentrations from 5.0μg/L to 500.0μg/L, and the correlation coefficients of more than 0.9986, the limits of detection (LOD, S/N=3) between 0.12μg/kg and 1.07μg/kg and the limits of quantification(LOQ, S/N=10) between 0.40μg/kg and 3.57μg/kg. At 3 different standard addition levels of 5.0,0.0, and 20.0μg/kg, the average recoveries of 19 kinds of PCBs was between 79.6% and 103.4%, and the intra-day relative standard deviation was between 2.2%~9.6%. While at 3 different standard addition levels of 20.0,0.0, and 200.0μg/kg, the average recoveries of 19 kinds of PCBs was between 77.4% and 104.6% and the inter-day relative standard deviation was between 2.7% and 9.8%. It is indicated that, the developed method is accurate, sensitive and reliable and suitable for the monitoring and detection of 19 kinds of PCBs in aquatic products.