Contamination of soils with non-aqueous phase liquids (NAPL) constitutes a serious geo-environmental problem, given the toxicity level and high mobility of these organic compounds. To develop effective decontamination methods, characterisation and identification of contaminated soils are needed. The objective of this work is to explore the potential of dielectric permittivity measurements to detect the presence of NAPLs in soils. The dielectric permittivity was measured by Time Domain Reflectometry method (TDR) in soil samples with either different volumetric content of water (w) and NAPL (NAPL) or at different stages during immiscible displacement test carried out with two different flushing solutions. A mixing model proposed by Francisca and Montoro, was calibrated to estimate the volume fraction of contaminant present in soil. Obtained results, showed that soil contamination with NAPL and the monitoring of immiscible fluid displacement, during soil remediation processes, can be clearly identified from dielectric measurements.