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In this work, electroactive biofilms of Bacillus subtilis (B. subtilis) or Escherichia coli (E. coli) were supported on functionalized biocarbon (AB7-F), which was synthesized from waste leather and was used as catalysts to develop bioanodes for microbial fuel cells (MFCs). This way, bioanodes were fabricated and further evaluated in a three-electrode cell using pharmaceutical wastewater (PWW) as substrate. The electrochemical measurements showed a higher performance of the bioanode based on AB7-f+ B. subtilis to oxidize organic matter from PWW. The polarization curves in the dual-chamber MFC showed that AB7-f+ B. subtilis bioanode can generate an open circuit voltage of 602 mV and a power density of 77 mW m−2. During long-term tests of the MFC, a variation in performance was observed, with a maximum of 96.3 mW m−2 on day 7. Such variation was attributed to the development of more stable biofilm as well as consumption of some compounds metabolized by bacteria grown on the bioanode. The results showed that AB7-f+ B. subtilis can be used as bioanode for MFCs with PWW as substrate removing around 45% of the chemical oxygen demand (COD). [ABSTRACT FROM AUTHOR]