In order to collect baseline information on the environmental occurrence of volatile organic compounds (VOCs) in groundwater in East China, shallow groundwater samples were collected from five alluvial plains in East China in 2008 to 2009. All samples were analyzed for 54 VOCs representing a wide variety of uses and origins. Sampling sites were mainly selected in the areas to be susceptible to contamination from human activities in terms of previous hydrogeological survey. The data of all samples showed a variety of different hydrogeological systems with potential sources of VOCs, with 36 of the 54 VOCs being found. The most frequently detected compounds include naphthalene (56.9%), chloroform (16.9%), 1,2-dichloroethane (16.2%), 1,2-dichloropropane (13.1%), and 1,2,3-trichlorobenzene (12.3%). The concentrations of methylene chloride, 1,2-dichloroethane, carbon tetrachloride, trichloroethene, 1,2-dichloropropane, and tetrachloroethene exceeded the relating drinking water standards. Future work will be needed to identify those factors that are most important in determining the occurrence and concentrations of VOCs in groundwater in China.