The molecularly imprinted polymer coating fibers with 3, 4-dichlorophenylacetic acid as template molecule, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as crosslink agent, 2, 2'-Azobis(2-methylpropionitrile) as initiator were obtained by in-situ polymerization method. And they were filled into a stainless steel needle to prepare the NTD for analysis of polychlorinated biphenyls in industrial wastewater. The synthesis conditions of molecularly imprinted polymer coating, such as functional monomer were optimized. Under the optimal conditions, the linear range of PCB28 and PCB52 was 0.02~500 μg/L, and that of PCB118, PCB153 and PCB180 was 0.05~500 μg/L. The correlation coefficient (r) was between 0.9912 and 0.9959, and the detection limit was between 0.0045~0.014 μg/L. The prepared NTD with molecularly imprinted polymer coating can selectively adsorb PCBs in complex samples with high extraction efficiency. The spiked recoveries were 90.89%~98.93% with relative standard deviations (RSDs) less than 9.3%.