Aiming at the technical problem that it is difficult to distinguish “lithological low resistance” from “water-bearing low resistance” in the limestone aquifer of Taiyuan Formation at the floor of Group A coal face in Huainan mining area, taking the 13421 working face of Gubei Coal Mine as the engineering background, the application research of dual-frequency induced polarization (DFIP) method was systematically carried out by adopting the technical route of “numerical simulation-physical simulation-field detection-comprehensive verification”. The results of numerical and physical simulation show that water-rich areas present the typical response characteristic of “low resistivity + high frequency dispersion rate”, which verifies the feasibility of this method to solve “low resistance multi-interpretability” from the theoretical level. Moreover, the positioning accuracy of dual-frequency IP omni-directional detection technology for anomalies is significantly better than that of traditional methods. In the field of 13421 working face of Gubei Coal Mine, fan-shaped scanning with multiple measuring points was arranged through the dual-frequency IP detection system, and two water-rich abnormal areas were successfully delineated within the depth of 70 m under the floor. Through drilling verification and comparative analysis of three-dimensional electrical method, the delineated abnormal areas have a high degree of coincidence with borehole water outflow points, and the water-rich identification accuracy is significantly superior to that of traditional geophysical exploration technologies. Meanwhile, it is confirmed that the water conductivity of faults in the working face is weak, which is consistent with the actual on-site exposure. The research shows that the dual-frequency IP method can realize the accurate detection and positioning of limestone water hazards at the floor of group A coal, and provide reliable technical support for the safe and efficient mining of Group A coal in Huainan mining area.