Air toxics, also well-known as hazardous air pollutants (HAPs), have significant health effects on human health and are of great concern. This paper studied a number of hazardous air pollutants in an industrial and metropolitan complex area in order to determine their ambient abundance and potential health impacts. The target pollutants in this study are benzene, formaldehyde, 1,3-butadiene, arsenic, 2,3,7,8-TCDD, and diesel particulate matter (DPM). A cancer risk assessment was conducted to determine the health effects of exposure to the six HAPs by using the AERMOD model. Results indicated that the emission of benzene, formaldehyde, 1,3-butadiene, arsenic and DPM was 184.5; 227.3; 68.0; 238, and 316 ton year–1, respectively, and the emission of 2,3,7,8-TCDD was 4,994 mg-TEQ year–1. Benzene (86%), formaldehyde (69%), and 1,3-butadiene (77%) were mainly emitted from on-road mobile sources. Arsenic (70%) and 2,3,7,8-TCDD (about 100%) were mainly emitted from stationary sources and DPM was emitted from diesel engines, port operations and ocean-going vessels. Spatial air toxic distribution indicated that the highest concentration of DMP, benzene, formaldehyde, and 1.3-butadiene occurred on the highway and in the downtown district due to their high traffic volume. DPM occupied more than 80% of total cancer risk in the region, followed by 1,3-butadiene, benzene, formaldehyde, arsenic, and 2,3,7,8-TCDD. In the industrial and residential complex area, about 99% of the cancer risk stemmed from on-road vehicles and port operations due to hazardous air pollutant emissions, especially DPM. The control scenario was made huge efforts to reduce the emission, however the results indicated only reduced the overall cancer risk assessment by 10%–15%. Policy makers have to think carefully about whether implementing the kind of emissions regulations simulated in this control scenario will need to be enhanced with additional measures to further reduce the risk of air pollution for human health.