Polycyclic aromatic hydrocarbons (PAHs) and their halogenated derivatives (HPAHs) can be unintentionally formed and released during industrial thermal processes. However, information on internal exposure and health risks of PAHs and HPAHs for thermal industry workers is very limited. In this study, serum samples from 220 aluminum smelter workers in East China were analyzed, and the relationship between the levels of these pollutants and various health indicators was also assessed. The workers had markedly higher serum concentrations of PAHs and HPAHs than the controls. The serum concentrations of ∑13PAHs and ∑9HPAHs increased with increasing age and occupational exposure duration in male workers. A positive correlation was observed between the ∑13PAH and ∑9HPAH serum concentrations, and the concentration of ∑13PAHs was approximately 50 times higher than that of ∑9HPAHs. For benzo[a]pyrene equivalent (BaPeq)-based risk assessment, the contribution of PAHs and HPAHs to the risk was 80 % and 20 % in the workers. PAHs and HPAHs showed a positive association with pulmonary hypofunction, hypertension and abnormal electrocardiogram. This study indicates occupational exposure to these toxic pollutants remains a significant issue and provides evidence that elevated serum levels of ∑13PAHs and ∑9HPAHs may be associated with an increased risk of lung and cardiovascular diseases.