Microbial fuel cells (MFCs) are an emerging technology which show promise to concomitantly clean wastewater and produce electricity. Microorganisms in a MFC utilize organic matter as an energy source and, in the absence of oxygen, will use an electrode as a terminal electron acceptor. Shewanella oneidensis is an eletrogenic microorganism whose electron transfer ability is afforded by multiple cytochrome/heme bearing proteins in its outer membrane. These proteins are responsible for electron transfer from intracellular metabolites to an extracellular electron acceptor. Past studies have shown improved MFC performance with Shewanella upon incorporation of membrane intercalating conjugated oligoelectrolytes (COEs). In an effort to further improve MFC performance, a new COE (abbreviated herein as DSFO) has been designed based on the known redox behavior of Shewanella’s transmembrane proteins and the first generation of COEs. Unlike the previous generation of COEs, DSFO was designed to possess redox activity in the typical operating voltage range of a MFC. DSFO shows improved current production in MFCs compared to the first generation of compounds. Employing in situ cyclic voltammetry, we have shown that DSFO can catalyze electron transfer when a MFC is operated near the oxidation half-potential of DSFO. With the use of in situ impedance spectroscopy, we have shown that DSFO greatly reduces the diffusion resistance of a MFC as well as marginally reducing the charge transfer resistance. Most interestingly, DSFO is able to recover the electrogenic character of mutant bacterial strains lacking key electron transfer proteins. These results suggest the ability of DSFO to act as an electron transfer conduit and a protein surrogate. In a broader context, this research effort has direct implication in the large-scale implementation of MFCs and could offer an opportunity to impart electrogenic capabilities to non-electrogenic microorganisms via the use of redox active COEs.