Lead release in a lead (Pb, anode)-iron oxide (α-Fe2O3, cathode) galvanic system was studied under the influence of synthetic extracellular polymeric substances (sEPS). Sodium alginate, bovine serum albumin (BSA), and cytochrome c represented extracellular polysaccharides, proteins, and electrochemically active components, respectively. Microbiologically influenced corrosion was investigated using sEPS and pelleted and resuspended Pseudomonas aeruginosa cells. Relative to the anaerobic inorganic control, Pb release increased by 156, 202, and 198 μg/L when sEPS was present on the cathode side at 200 mg/L (100 mg/L alginate + 100 mg/L BSA), 400 mg/L (200 mg/L alginate + 200 mg/L BSA), and 200 mg/L with 123.84 mg/L cytochrome c, respectively, under anaerobic conditions. When the cathode was aerated, Pb release increased by 75, 260, and -71 μg/L under the aforementioned conditions, all relative to the aerated inorganic control. When sEPS was instead present on the anode side, sEPS caused localized corrosion on Pb and resulted in higher Pb release than predicted by electric current. P. aeruginosa generally enhanced corrosion; when cells were dosed in the anode side, part of the oxidized Pb was immobilized by cells or organic compounds adhered to the electrodes.