In order to study the dehydrogenation of ethylbenzene to styrene, epitaxial iron oxide model catalyst films with Fe3O4(111), α-Fe2O3(0001) and KFe x O y (111) stoichiometry were prepared in single crystal quality on Pt(111). They were investigated using surface science techniques before and after atmospheric pressure reaction experiments in a newly designed single crystal flow reactor. As expected from low-pressure measurements, Fe3O4(111) is catalytically inactive. The catalytic activity of α-Fe2O3(0001) starts after an activation period of about 45 min. After that, the surface is essentially clean but shows a high concentration of defects. On the potassium-promoted films, however, the activation period is much longer, the activity then is higher and the surface gets covered completely with carbon and oxygen during reaction. This indicates a different reaction pathway on the promoted films with a carbon–oxygen species as catalytically active species.