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Acid mine drainage (AMD) is a typical source of environmental pollution ascribing to its characteristics of high acidity and heavy metal content. Currently, most strategies for AMD treatment merely focus on metal removal rather than metal recovery. However, bioelectrochemical system (BES) is a promising technology to simultaneously remove and recover metal ions from AMD. In this study, both cupric ion and cadmium ion in simulated AMD were effectively recovered by BES inoculated with a novel exoelectrogen, <i>Pseudomonas</i> sp. E8, that was first isolated from the anodic electroactive biofilm of a microbial fuel cell (MFC) in this study. <i>Pseudomonas</i> sp. E8 is a facultative anaerobic bacterium with a rod shape, 0.43&#8722;0.47 &#956;m wide, and 1.10&#8722;1.30 &#956;m long. <i>Pseudomonas</i> sp. E8 can agglomerate on the anode surface to form a biofilm in the single-chamber MFC using diluted Luria-Bertani (LB) medium as an energy substrate. A single-chamber MFC containing the electroactive <i>Pseudomonas</i> sp. E8 biofilms has a maximum output voltage of 191 mV and a maximum power density of 70.40 mW/m², which is much higher than those obtained by most other exoelectrogenic strains in the genus of <i>Pseudomonas</i>. Almost all the Cu²⁺ (99.95% &#177; 0.09%) and Cd²⁺ (99.86% &#177; 0.04%) in simulated AMD were selectively recovered by a microbial fuel cell (MFC) and a microbial electrolysis cell (MEC). After the treatment with BES, the high concentrations of Cu²⁺(184.78 mg/L), Cd²⁺(132.25 mg/L), and total iron (49.87 mg/L) in simulated AMD were decreased to 0.02, 0.19, and 0 mg/L, respectively. Scanning electron micrograph (SEM), energy dispersive X-ray spectrometry (EDXS) and X-ray diffraction (XRD) analysis indicate that the Cu²⁺ and Cd²⁺ in simulated AMD were selectively recovered by microbial electrochemical reduction as Cu⁰ (together with trace amounts of Cu₂O) or Cd⁰ on the cathode surface. Collectively, data suggest that <i>Pseudomonas</i> sp. E8 has great potential for AMD treatment and metal recovery.