This study aimed at developing a simple and accurate method for determination of emerging chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) in fish by stable isotope dilution gas chromatography tandem mass spectrometry. Fish samples were extracted by improved accelerated solvent extraction (ASE) method. Matrix effects were observed, and matrix-matched calibration was verified with good intra-day and inter day precisions (lower than 16.1% and 15.1% respectively). Method detection limits were 0.10–5.62 ng g−1 (dry weight) with satisfactory linearity, and recoveries ranged from 50% to 150%, with relative standard deviation values less than 18.5% at different concentration levels. This improved ASE method was proved to be suitable for analyzing Cl-PAHs in fish samples, with good analytical selectivity, linearity, recovery and precision. Furthermore, the composition analysis revealed that chlorinated compounds of phenanthrene, pyrene and acenaphthene were dominated in Cl-PAHs contaminants. The correlationship between the pollution of Cl-PAHs and their corresponding parent structures in fish samples was also analyzed in detail.