Polycyclic aromatic hydrocarbons (PAHs) are a group of organic compounds that are both toxic and hazardous to human health and ecological systems. In recent work, a novel analytical strategy based on the chemometric-assisted HPLC-DAD method was proposed for the quantification and source apportionment of eight PAHs in PM10 samples. Compared to traditional chromatographic methods, this approach does not require the purification of complex PM10 samples. Instead, it utilizes a mathematical separation method to extract analytes’ profiles from overlapping chromatographic peaks, enabling precise quantification of PAHs in PM10. Firstly, 40 PM10 samples collected in Loudi city during two sampling periods were used for analysis. Subsequently, the second-order calibration method based on alternating trilinear decomposition (ATLD) was employed to handle the three-way HPLC-DAD data. Finally, the pollution sources of PAHs were analyzed by the feature component analysis method according to the obtained relative concentration matrix. For the validation model, the average recoveries of eight PAHs were between (88.8 ± 7.6)% and (105.6 ± 7.5)%, and the root-mean-square errors of prediction ranged from 0.03 μg mL−1 to 0.47 μg mL−1. The obtained limits of quantification for eight PAHs were in the range of 0.0050 μg mL−1 to 0.079 μg mL−1. For actual PM10 samples, results of the feature component analysis indicated that the main source of PAHs in PM10 may be traffic emissions and coal combustion. In summary, the proposed method provided a new and rapid analysis method for the accurate determination and source apportionment of PAHs in atmospheric aerosols.