Legacy mining industry has left a large number of tailings ponds exposed to water and wind erosion that causes serious environmental and health problems. Prior to rehabilitation actions a deep sampling of the materials infilling the pond used to be necessary. Thus, the primary objective of this study is to demonstrate the usefulness of the Electrical Resistivity Tomography (ERT) method as a non-invasive tool to determine the physicochemical composition of mine tailings ponds, enabling more efficient and low-cost surveys. To achieve this objective, three ERT profiles and three boreholes in each profile were carried out, from each borehole three waste samples from differents depths were collected and a geochemical characterization of the samples was carried. In order to estimate the composition of the infilling wastes in tailing ponds from electrical resistivity measures, several regression models were calculated for different physicochemical properties and metal concentrations. As a result, a high resistivity area was depicted in profiles G2 and G3 while a non-resistive area (profile G1) was also found. Relationships among low resistivity values and high salinity, clay content and high metal concentrations and mobility were established. Specifically, calibrated models were obtained for electrical conductivity, particles sizes of 0.02-50 µm and 50-2000 µm, total Zn and Cd concentration, and bioavailable Ni, Cd and Fe. Therefore, the ERT technique could be considered as a useful tool for mine tailings ponds characterization, and it can be used to estmate some physicochemical properties and metal concentrations of this mine waste.