The occurrences, distributions, and risks of 55 target volatile organic compounds (VOCs) in water, sediment, sludge, and soil samples taken from a chemical industrial park and the adjacent area were investigated in this study. The Σ55-VOCs concentrations in the water, sediment, sludge, and soil samples were 1.22–5449.21 μg L−1, ND–52.20 ng g−1, 21.53 ng g−1, and ND–11.58 ng g−1, respectively. The main products in this park are medicines, pesticides, and novel materials. As for the species of VOCs, aromatic hydrocarbons were the dominant VOCs in the soil samples, whereas halogenated aliphatic hydrocarbons were the dominant VOCs in the water samples. The VOCs concentrations in water samples collected at different locations varied by 1–3 orders of magnitude, and the average concentration in river water inside the park was obviously higher than that in river water outside the park. However, the risk quotients for most of the VOCs indicated a low risk to the relevant, sensitive aquatic organisms in the river water. The average VOCs concentration in soil from the park was slightly higher than that from the adjacent area. This result showed that the chemical industrial park had a limited impact on the surrounding soil, while the use of pesticides, incomplete combustion of coal and biomass, and automobile exhaust emissions are all potential sources of the VOCs in the environmental soil. The results of this study could be used to evaluate the effects of VOCs emitted from chemical production and transportation in the park on the surrounding environment.