The effective detection and monitoring of mining tailings’ leachates (MTLs) plays a pivotal role in environmental protection and remediation efforts. Electrical resistivity tomography (ERT) is a non-invasive technique widely employed for mapping subsurface contaminant plumes. However, the efficacy of ERT depends on selecting the optimal electrode array for each specific case. This study addresses this challenge by conducting a comprehensive review of published case studies utilizing ERT to characterize mining tailings. Through numerical simulations, we compare the imaging capabilities of commonly used electrode configurations, six ERT arrays, aiming to identify the optimal array for MTLs’ detection and monitoring. In addition, field surveys employing ERT were conducted at the El Mochito mine tailings site to detect zones saturated with leachates within the tailing storage facilities (TSFs). The findings indicate that the “Wenner-Schlumberger” array exhibits superior data resolution for MTL detection. However, the choice of the optimal electrode array is contingent on factors such as survey location, geological considerations, research objectives, data processing time and cost, and logistical constraints. This study serves as a practical guide for selecting the most effective electrode array in the context of pollutant penetration from mining tailings, employing the ERT technique. Furthermore, it contributes valuable insights into characterizing zones saturated with mining tailing leachates within the TSFs, providing a solid foundation for informed environmental management and remediation strategies.