The current projects for the disposal of high-level radioactive waste rely on underground burial and confinement by metallic envelopes that are susceptible to corrosion processes. The impact of microbial activity must be fully clarified in order to provide biological parameters for predictive reactive transport models. This study investigates the impact of hydrogenotrophic iron-reducing bacteria (Shewanella oneidensis strain MR-1) on the corrosion rate of carbon steel under simulated geological disposal conditions by using a geochemical approach. It was found that corrosion damage changes mostly according to the experimental solution (i.e., chemical composition). Magnetite and vivianite were identified as the main corrosion products. In the presence of bacteria, the corrosion rate increased by a factor of 1.3 (according to weight loss analysis) to 1.8 (according to H2 measurements), and the detected amount of magnetite diminished. The mechanism likely to enhance corrosion is the destabilization and dissolution of the passivating magnetite layer by reduction of structural Fe(III) coupled to H2 oxidation.