This work presents the results of an assessment of the existence and concentration of 13 volatile organic compounds (VOCs) in groundwaters from 14 hydrological basins in Sicily (25,710km (2)). On the basis of hydrological, hydrogeochemical and geological studies, 324 sampling points were selected. All groundwater sampled were collected twice, from October to December 2004 and from February to May 2005, and were analysed to determine the concentration and spatial distribution of the VOCs in the aquifers. The need to analyze a large number of samples in a short space of time so as to obtain quantitative analyses in trace concentration levels spurred us to create a new analytical method, both simple and sensitive, based on HS-SPME/GC/MS. The concentrations of VOCs measured in industrial and intensive agricultural unconfined aquifers were greater than those found in other aquifers. Tetrachloroethylene, chloroform, trichloroethylene and 1,2-dichloropropane were the most frequently detected VOCs. However, they exceeded the guideline values proposed by the EU in only three aquifers located near to industrial and intense agricultural areas.