generation, [3,4] while microbial electrosynthesis platforms employ electron flux into cells to drive metabolic reduction of substrates to more valuable chemical products. [5,6] Practical implementations of BES technologies are challenged by interfacial contact(s) that limit efficient extracellular electron transfer (EET) and by low bacterial loading. [7][8][9] Substantial efforts have therefore been centered on developing 3D electrodes that maximize surface area with integrated microbes. Two main strategies have been reported: first, integration of microbes in pre-prepared 3D electrodes that afford large surface areas, [10][11][12][13][14] and second, in situ formation of soft conductive materials/bacteria composites. [15][16][17][18][19] The first strategy grants flexible design of the conductive matrix separately, but may suffer from low infiltration, clogging, and inhomogeneous distribution of cells within the 3D electrode network. [15] The second strategy circumvents the aforementioned problems, yet remains generally underexplored due to the lack of suitable materials and biocompatible conditions for in situ formation of the synthetic matrix. A representative example of this second approach is the bioreduction of graphene oxide (GO) by Shewanella oneidensis MR-1 to form a 3D macroporous rGO/bacteria hybrid. [16] In another report, S. oneidensis MR-1 was encapsulated in a spontaneously formed hydrogel comprising a ferrocene-functionalized phospholipid polymer. [17] Electropolymerization of polypyrrole and PEDOT:PSS with S. oneidensis MR-1 provides yet another representative method to create conductive hybrid biofilms. [18,19] Conjugated polyelectrolytes (CPEs) can be designed to be water-soluble and thereby offer opportunities for in situ integration with bacteria in aqueous media. [20][21][22] A p-type CPE capable of self-assembly into a 3D conductive matrix with S. oneidensis MR-1 was recently reported. [21] The π-conjugated backbone undergoes facile redox cycling-electrochemical doping (oxidation) by the electrode and de-doping by S. oneidensis MR-1. The larger number of cells accessible to the external electrode through the CPE network leads to increases in biocurrent collection. Building on this foundation, we sought a new CPE material that can facilitate the reverse direction of EET to ultimately achieve microbial electrosynthesis. Noteworthy, such Microbial electrosynthesis-using renewable electricity to stimulate microbial metabolism-holds the promise of sustainable chemical production. A key limitation hindering performance is slow electron-transfer rates at bioticabiotic interfaces. Here a new n-type conjugated polyelectrolyte is rationally designed and synthesized and its use is demonstrated as a soft conductive material to encapsulate electroactive bacteria Shewanella oneidensis MR-1. The self-assembled 3D living biocomposite amplifies current uptake from the electrode ≈674-fold over controls with the same initial number of cells, thereby enabling continuous synthesis of succinate from fumarate. S...