The objectives of this study are to investigate the volatile organic compound (VOC) distribution using passive samplers and to assess the resulting health risks in a high-tech science industrial park. With the advantages of passive sampling techniques, long-term and wide-area samples are collected. The results show TVOC concentrations in summer, fall, winter, and spring are 7.14 ± 5.66 ppb, 18.17 ± 5.81 ppb, 10.30 ± 3.54 ppb, and 14.56 ± 4.53 ppb, respectively; those on weekdays and weekends are 14.36 ± 6.80 ppb and 9.87 ± 4.86 ppb, respectively; and those in industrial and residential zones are 12.97 ± 0.39 ppb and 11.13 ± 0.68 ppb, respectively. Based on concentration variations, and benzene, toluene, ethylbenzene, and xylene ratios, we can resolve the source origins. Health risks are assessed based on the resulting concentrations. In the case of non-cancer chronic effects, long-term exposure to these concentrations does not support there is a risk of adverse health effects. However, potential cancer risks of exposure to these concentrations may occur, especially to carbon tetrachloride and benzene. By applying this study's procedures, information on VOC concentration distribution, source identification, and health assessment can be obtained and they are applicable to similar studies.