A petrochemical complex located in central Taiwan is a major emission source of air pollutants locally. Among these air pollutants, it is concern that the health effects of exposure to heavy metal because of its toxicity and persistency. Therefore, we conducted a biological monitoring study to investigate the effect of heavy metal pollutants on inhabitants around this petrochemical complex. According to the distance and the wind direction from the petrochemical complex, the study area was divided into high exposure (HE) and low exposure (LE) areas, and a total of 673 study subjects who aged above 35 years old living in HE and LE areas were recruited to be collected urine sample and personal information by health screen and questionnaire administration. The concentrations of ten kinds of urinary heavy metals were analyzed by inductively coupled plasma mass spectrometry. After adjusting for age, gender, socioeconomic status, smoking, dietary habits and other potential confounders, the multiple linear regression models showed that the urinary levels of vanadium, manganese, arsenic and strontium of inhabitants in HE area were significantly higher than those of inhabitants in LE area. This study indicated the potential effects of emitted metal pollutants from a petrochemical complex on the residents nearby.