The effective techniques for remediation of sites polluted by dense non-aqueous phase liquids (DNAPLs) remains a challenge. Among the various technical monitoring methods, there is an increasing interest in studying the geophysical characteristics of contaminated soils, as indicators of the progress in clean-up programs. This work sought to investigate the variation of the electrical complex resistivity and the relative permittivity by analyzing the results obtained from spectral induced polarization (SIP) and time domain reflectometry (TDR). Different series of measurements during drainage and imbibition of DNAPLs in porous media were done to validate the clean-up process on sites polluted by DNAPLs. Therefore, a methodology based on laboratory work was designed and carried out to study the electrical complex resistivity (both in magnitude and phase) in the frequency range 0.183 Hz to 20 kHz, and the relative dielectric permittivity at 70 MHz. The experiments were done on small 1D cells. In these cells, glass beads were used as a porous medium. Two different fluid couples, i.e., coal tar (CT)/water and canola oil (CO)/salty ethanol (SE), were used to produce two-phase flow. Our findings highlight that due to the high resistivity of CO and CT, an increase in water saturation led to decrease in amplitude and phase. Saturation change of SE had the same effect on resistivity but no relationship was found for phase and saturation for the mixture CO and SE. It is also showed that the complex resistivity and relative permittivity measurements were compatible with generalized Archie's law and complete complex refractive index method (CRIM) model as two empirical models for defining the correlation between the electrical resistivity, relative permittivity, and saturation of each phase in the multiphase porous medium.