Background: Groundwater contamination with chlorinated hydrocarbons (CLHCs), particularly with tetrachloroethylene (PCE) and trichloroethylene (TCE), which are used in industry for degreasing and cleaning, can be considered a serious problem concerning the entire world. In addition to conventional groundwater monitoring from a network of wells, several screening methods have been proposed to identify and delineate groundwater contamination with volatile organic compounds (VOCs), such as soil gas measurement, bioindicators, direct-push technologies or geophysical techniques. The main objectives of this study were to confirm the feasibility of active soil gas screening for the characterisation of groundwater contamination with CLHCs under the wider area of the former refrigerator manufacturer (city of Zlaté Moravce, western Slovakia) and to evaluate the human health risks through exposure to CLHCs present in groundwater. Methods: a conventional site investigation based on concentration measurements using gas chromatography-mass spectrometry from monitoring wells and soil gas measurements using a portable photo-ionisation detector device were applied. Results: The chemical analyses showed the persistent contamination of groundwater, with PCE, TCE and other CLHCs, such as cis-1,2-dichloroethylene (cis-DCE) or 1,1,2-trichloroethane (TCA), being most severe in the zone of the former factory (up to 2690, 83,900, 6020 and 156 µg/L for PCE, TCE, cis-DCE and TCA, respectively), but also extended into the residential zone located 600 m along the groundwater flow line. Soil gas measurements of VOCs and other chemical parameters (methane (CH4), total petroleum (TP), carbon dioxide (CO2) and oxygen (O2)) from a densely designed network of sampling points (n = 300) helped trace the current state of groundwater contamination. Spatial distribution maps of VOCs concentrations in soil gas clearly marked the areas of the highest CLHCs concentrations in groundwater. Principal component analysis (PCA) confirmed a significant correlation of VOCs and CLHCs with the first principal component, PC1, explaining up to 84% of the total variability of the concentration data, suggesting that VOCs in soil gas were a suitable marker of the extent of groundwater contamination with CLHCs. Despite severe groundwater contamination with CLHCs reaching residential areas, local residents were not exposed to non-carcinogenic risks, but a potential carcinogenic risk was present. Conclusions: based on the results, it could be confirmed that soil gas screening is an efficient and quick tool for identifying the sources of groundwater contamination with CLHCs as well as the level of this contamination.