Identification of heteroatom compoundscontaining chlorineandoxygen in plastic waste pyrolysis oil (PWPO) is significant for processing.A quantitative method for 32 chlorinated hydrocarbons in PWPO wasestablished by a gas chromatography-electron capture detector. Eightchlorinated hydrocarbons were found in PWPO, accounting for 14.0%of the total chlorine, with 1,2-dichloroethane having the highestamount. 73 compounds in the polar fraction of PWPO were identifiedusing solid phase extraction and gas chromatography-mass spectrometry.The proportions of these compounds in the polar fraction decreasedin the order of esters, nitriles, ketones, acids (including anhydride),chloroesters, phenols, alcohols, ethers, aldehydes, trienes, and siloxanes.The polar fraction contained nine chlorides. All of these chlorideswere in the form of 2-chloroethyl ester, and 1,4-benzenedicarboxylicacid, di-2-chloroethyl ester, had the highest proportion among thenine chlorides. Finally, the formation pathways of 2-chloroethyl esterswere illustrated. These results would provide support for the developmentof a clean processing technology for PWPO.