In this study, a coupled membrane-free microbial fuel cell (MFC) with permeable reactive barrier (PRB) was reported and its treatment performance and electricity generation for acid mine drainage (AMD) were examined. The pilot-scale continuous flow MFC-PRB was operated for five periods at a hydraulic retention time of 48.0 h, and the average sulphate removal percentages of 51.2%, 39.8%, and 33.1% were obtained in effluent of 1,000, 2,000, 3,000 mg/l, respectively. More than 99.5% of the initial concentrations of Cu²⁺, Zn²⁺, and Pb²⁺ were removed, resulting in concentrations of those elements of 0.01-0.05 mg/l in the effluent. The results demonstrated that the MFC-PRB holds a potential capacity for remediation of AMD.