Recent advances in coupling light-harvesting microorganisms with electronic components have led to a new generation of biohybrid devices based on microbial photocatalysts. These devices are limited by the poorly conductive interface between phototrophs and synthetic materials that inhibit charge transfer. This study focuses on overcoming this bottleneck through the metabolically-driven encapsulation of photosynthetic cells with a bio-inspired conductive polymer. Cells of the purple non sulfur bacterium Rhodobacter sphaeroides were coated with a polydopamine (PDA) nanoparticle layer via the self-polymerization of dopamine under anaerobic conditions. The treated cells show preserved light absorption of the photosynthetic pigments in the presence of dopamine concentrations ranging between 0.05–3.5 mM. The thickness and nanoparticle formation of the membrane-associated PDA matrix were further shown to vary with the dopamine concentrations in this range. Compared to uncoated cells, the encapsulated cells show up to a 20-fold enhancement in transient photocurrent measurements under mediatorless conditions. The biologically synthesized PDA can thus act as a matrix for electronically coupling the light-harvesting metabolisms of cells with conductive surfaces.