Bioelectrochemical systems (BES) are emerging as potential technologies that can remediate acid mine drainage (AMD) by cathodic reduction of sulfates to metal sulfides. This study evaluated bioelectrochemical remediation of sulfate rich AMD at two applied cathode potentials; BES-1: −1.0 V and BES-2: −0.8 V. Sulfate reducing bacteria were selectively enriched to be used as biocatalyst in BES. Initially, lactate was fed as carbon source and switched to chemolithoautotrophy with only CO2-fed conditions. Both BESs were operated at 3±0.2 g/l of sulfate with synthetic AMD (SAMD) fed first, and gradually changed to 50% AMD from mining site with 50% SAMD. Sulfate reduction was relatively higher with BES-1: 82% than BES-2: 76% coupled with sulfidogenesis. Interestingly, acetogenesis (BES-1: 2.12±0.2 g/l, BES-2: 1.9±0.2 g/l) was also noticed with high reduction currents (BES-1&2: >-70 mA). Microbiome community analysis revealed the dominant presence of sulfate reducers, acetogens, syntrophic bacteria and Methanobacterium, probing microbial synergy aiding sulfate reduction. An added advantage was the iron-sulfide (FeS) particles formation on cathode, which might have contributed to increased reduction currents. This study reveals insights into microbial synergy for autotrophic sulfate reduction within mixed microbiome communities along with the impact of FeS particles as conducive facilitator for electron transfer in BES, thereby enhancing electrosynthetic acetate production.