The biological sulfur cycle is closely related to iron corrosion in the natural environment. The effect of the sulfur-oxidising bacterium Ectothiorhodospira sp., named PHS-Q, on the metal corrosion behaviour rarely has been investigated. In this study, the corrosion mechanism of Q235 carbon steel in a PHS-Q-inoculated medium is discussed via the characterization of the morphology and the composition of the corrosion products, the measurement of local corrosion and the investigation of its electrochemical behaviour. The results suggested that, initially, PHS-Q assimilates sulfate to produce H2S directly or indirectly in the medium without sulfide. H2S reacts with Fe2+ to form an inert film on the coupon surface. Then, in localised areas, bacteria adhere to the reaction product and use the oxidation of FeS as a hydrogen donor. This process leads to a large cathode and a small anode, which incurs pitting corrosion. Consequently, the effect of PHS-Q on carbon steel corrosion behaviour is crucial in an anaerobic environment.