Mining activity in the Iberian Pyrite Belt, on the south‐west of the Iberian Peninsula, has generated a great amount of mine tailing ponds, which once the extractive activity is finished, are abandoned and become a serious environmental problem. Here we present the results of applying the electrical resistivity tomography (ERT) technique to characterize the abandoned mine ponds in two sites: Monte Romero and Mina Concepción. ERT has allowed us to determine both the general geometry of the pond’s base and the maximum thickness of the mine tailings. In all cases, the resistivity contrast between the infilling and the bedrock is high enough to clearly define the bottom pond boundary. The low‐resistivity values (lower than 5 Ωm) obtained for the infilling are explained by the high concentration of pyrite in the tailings and the occurrence of acid waters. Whereas the Monte Romero mine pond is almost completely saturated with water, in Mina Concepción it has been possible to identify the presence of inner acid water flows, the outlet of which through the damaged dyke originates a spilling of acid waters to the Odiel River. No low‐resistivity water flows through the base of the ponds into the bedrock have been observed, indicating a good isolation of the base of the studied mine ponds.