Bioelectrochemical systems (BESs) such as microbial fuel cells (MFCs) present numerous benefits for the removal and recovery of heavy metals from industrial and municipal wastewater. This study evaluated the life cycle environmental impact of simultaneous hexavalent chromium (Cr(VI)) removal and bioelectricity generation in a dual chamber MFC. Results indicate a global warming potential (GWP) of −0.44 kg carbon dioxide (CO₂)-eq. per kg of chromium recovered, representing a total saving of up to 97% in comparison with existing technologies for the treatment of Cr(VI) laden wastewater. The observed savings in GWP (kg CO₂-eq.) reduced to 61.8% with the removal of the allocated credits from the MFC system's life cycle. Of all the various sub-systems considered within the chromium waste treatment plant, the MFC unit and the chromium metal recovery unit had the largest impact in terms of GWP (kg CO₂-eq.), non-renewable energy use (NREU) (MJ primary), and mineral extraction (MJ surplus). A statistical analysis of the results showed that an increase in chemical oxygen demand (COD) was associated with a reduction in GWP (kg CO₂-eq.), NREU (MJ primary), and terrestrial ecotoxicity (kg triethylene glycol equivalents into soil (TEG soil)-eq.). The life cycle assessment (LCA) output showed a high sensitivity to changes in the materials and construction processes of MFC reactors, indicating the need for further research into sustainable materials for MFC reactor construction. The observed interaction effects of process variables also suggest the need for combined optimization of these variables. Analysis with other types of metals is also important to further demonstrate the practical viability of metal removal through MFCs.