Efficient charge transfer across the biotic-abiotic interface is a significant obstacle for the integration of biological and electronic systems in high-performance microbial electrochemical systems (METs). Technologically relevant METs rely on the ability of microbes to undergo extracellular electron transfer (EET) to an electrode, however few species have the inherent ability to undergo this process. Most bacteria, for example, Eschericia coli, have non-existent or inefficient EET pathways. In an approach to modify the biotic-abiotic interface and create a pathway for charge transfer, membrane-insertion molecules characterized by an electronically delocalized, hydrophobic backbone-bearing pendant charged, hydrophilic functional groups, namely, conjugated oligoelectrolytes (COEs), are used. Previously, COEs have demonstrated increased performance of E. coli microbial fuel cells (MFCs) as well as increased anodic respiration in S. oneidensis. Mechanistic studies on the COE EET pathway in S. oneidensis have evidenced enhanced direct electron transfer via innate pathways in this species. While E. coli lacks any obvious homologues to the cellular components responsible for EET in S. oneidensis, current and power production are improved with COE modification by 6- and 10-fold, respectively. To better understand the origin of performance improvements in E. coli MFCs, contributions to current and power generation are deconvoluted into the performance contributions from the biofilm and planktonic cells. The mechanism of performance improvement with COE intercalation is found to be contingent on the direct contact of the microbe with an electrode. Thus, we were able to demonstrate a method of modifying the biotic-abiotic interface with the ability to induce an electrogenic behavior in a microorganism incapable of efficient EET, and this capability is maintained by the biofilm.