This study reports the significant mechanistic difference between binary-oxide antibacterial films with the same composition but different microstructures. Binary TiO2-FeOx films were found to present a faster bacterial inactivation kinetics under visible light irradiation than each single oxide acting independently. The interaction between the film active surface species and the bacteria within the disinfection period was followed by X-ray photoelectron spectroscopy (XPS) and provided the evidence for a redox catalysis taking place during the bacterial inactivation time. The optical and surface properties of the films were evaluated by appropriate surface analytical methods. A differential mechanism is suggested for each specific microstructure inducing bacterial inactivation. The surface FeOx plasmon resonance transferred electrons into the conduction band of TiO2 because of the Schottky barrier after Fermi level equilibration of the two components. An electric field at the interface between TiO2 and FeOx, favors the separation of the photo-generated charges leading to a faster bacterial inactivation by TiO2-FeOx compared to the bacterial inactivation kinetics by each of the single oxides.