The surface intertidal sediments in the Pearl River Estuary of China were analyzed from multiple perspectives, including the distribution characteristics, potential sources, and biological risks of polycyclic aromatic hydrocarbons (PAHs). The average concentration of PAHs, ranging from 73.68 ng/g to 933.25 ng/g, was 346.78 ng/g. PAHs are mainly composed of the 2- and 3-ring PAHs, with naphthalene (Nap), phenanthrene (Phe), pyrene (Pyr), benzo(g,h, i) perylene (Dib), fluoranthene (Flua), and indeno (1,2,3-c,d) pyrene (Ind) as the dominant constituents. The principal component analysis combined with multiple linear regression showed that petroleum combustion and biomass/coal combustion have contributed 52.78% and 40.53%, respectively, to the PAHs in intertidal sediments of Pearl River Estuary. The occurrence of adverse biological effects as a result of PAH contamination in the intertidal sediments of Pearl River Estuary has increased by 8% based on the mean value of the probable effect quotient.