The corrosive breakdown of thin iron films supported on silicon substrates under a number of conditions is presented—in particular to understand better how iron, and hence ferritic steel, behaves in a salty water environment. A combination of X-ray and neutron reflectometry was used to monitor the structures of both the metal and oxide surface layers and also organic corrosion inhibitors adsorbed at the iron/aqueous interface. A range of behaviour in seawater was observed, including complete dissolution and void formation under the metal surface. Importantly, two simple treatments—UV/ozone or soaking in ultrapure water—were found to significantly protect the iron surface for considerable lengths of time, although evidence of pitting corrosion began after around 10 days. The underlying causes of the efficacies of these treatments were further investigated using X-ray photoelectron spectroscopy. In addition, three potential corrosion inhibitors were investigated: (i) dodecyltrimethylammonium bromide (DTAB) demonstrated no ability to protect the surface; (ii) sodium dodecyl sulfate (SDS) appeared to accelerate corrosion; (iii) bis(2-ethylhexyl)phosphate showed an impressive level of protection (the neutron reflectometry results indicated a thick diffuse layer of surfactant of 23 % surface coverage). These findings have been interpreted in terms of preferential inhibitor adsorption at cathodic and anodic surface sites (depending on the nature of the inhibitor).