The applicability of radon (222Rn) measurements to delineate non-aqueous phase liquids (NAPL) contamination in subsoil is discussed at a site with lithological discontinuities through a blind test. Three alpha spectroscopy monitors were used to measure radon in soil air in a 25,000-m2 area, following a regular sampling design with a 20-m2 grid. Repeatability and reproducibility of the results were assessed by means of duplicate measurements in six sampling positions. Furthermore, three points not affected by oil spills were sampled to estimate radon background concentration in soil air. Data histograms, Q-Q plots, variograms, and cluster analysis allowed to recognize two data populations, associated with the possible path of a fault and a lithological discontinuity. Even though the concentration of radon in soil air was dominated by this discontinuity, the characterization of the background emanation in each lithological unit allowed to distinguish areas potentially affected by NAPL, thus justifying the application of radon emanometry as a screening technique for the delineation of NAPL plumes in sites with lithological discontinuities.