A high-performance liquid chromatographic method with a modified QuEChERS extraction for the determination of polycyclic aromatic hydrocarbons (PAHs) in blood serum was developed to investigate the internal exposure level and the carcinogentic toxicity contribution rate of PAHs for pregnant women in Nantong, China. Venous blood (n = 48) was collected in the local hospital and the internal exposure level of 16 PAHs and the contribution rate of carcinogenicity to pregnant women were analyzed. Among all of the detected PAHs, the detection rate of pyrene (77.08%) was the highest, followed by naphthalene (64.58%) and benzo[a]anthracene (BaA, 45.83%). The carcinogenicity contribution rate of BaA (37.37%) was the highest, followed by fluorene (32.96%) and acenaphthylene (22.01%). The results showed that many kinds of carcinogenic PAHs can be detected in the serum of pregnant women in Nantong city, among which BaA should be paid most attention because of its high internal exposure level and carcinogenic risk. Meanwhile, the origins of general PAHs in serum samples were analyzed using the characteristic ratio analysis method. The PAH pollution level of air samples (n = 42) during the collection time of blood samples was also analyzed to compare the possible correlations between the two different results.