Volatile organic compounds (VOCs) are involved in the formation of ozone formation, which plays a significant role in regional air contamination and poses a great threat to human health. The VOCs were collected from the urban area of Hefei city via an off-line sampling method (SUMMA canister) and determined by gas chromatography-mass spectrometer. The average concentrations of VOCs were 17.65 ± 28.36 ppbv, which were mainly contributed by aromatics (10.02 ± 13.37 ppbv), haloalkane (5.37 ± 8.90 ppbv), ally halide (1.25 ± 3.36 ppbv), and aryl halid (1.02 ± 2.73 ppbv). According to the principal component analysis, three major sources were identified, including solvent use, vehicle exhaust, and industrial release, accounting for 70.6% of the total variance of the data. Health risk assessment was utilized to evaluate the potential adverse health effects of the individual VOC. The total hazard ratio in the selected area was higher than 1, where could pose health threat to exposed population. The cancer risk for benzene, carbon tetrachloride, trichloromethane, and 1, 2-dichloroethane were 4.8 × 10, 4.5 × 10, 3.3 × 10, and 2.5 × 10, respectively, indicating definite health risks.