Biofilm formation on 304 stainless steel (S30400) does not necessarily result in an ennoblement of the corrosion potential. Instead, biofilms composed of aerobic and anaerobic bacteria from Gulf of Mexico water formed an anaerobic biofilm/metal interface and caused the corrosion potential to move in the negative direction. Biofilms from the same source containing photosynthetic diatoms in the presence of light produced aerobic biofilm/metal interfaces and a positive shift (ennoblement of the corrosion potential). Corrosion potentials of stainless steels exposed in natural seawater cannot be predicted without an understanding of the composition of the biofilm and its impact on interfacial chemistry. In this paper, measurements of corrosion potential, interfacial pH and dissolved oxygen have been correlated with SEM/EDAX surface analyses to evaluate the electrochemical behaviour of stainless steels exposed to Gulf of Mexico water. The interfacial chemistries that influence the corrosion potential are also discussed.