Sterilization is a prerequisite for biomedical devices before contacting the human body. It guarantees the lack of infection by eliminating microorganisms (i.e., bacteria, spores and fungi). It constitutes the last fabrication process of a biomedical device. The aim of this paper is to understand the effect of different sterilization methods (ethanol-EtOH, autoclave-AC, autoclave + ultraviolet radiation-ACUV and gamma irradiation-G) on the surface chemistry and electrochemical reactivity (with special attention on the kinetics of the oxygen reduction reaction) of CoCrMo and titanium biomedical alloys used as prosthetic materials. To do that, electrochemical measurements (open circuit potential, polarization resistance, cathodic potentiodynamic polarization and electrochemical impedance spectroscopy) and surface analyses (Auger Electron Spectroscopy) of the sterilized surfaces were carried out. The obtained results show that the effect of sterilization on the corrosion behavior of biomedical alloys is material-dependent: for CoCrMo alloys, autoclave treatment increases the thickness and the chromium content of the passive film increasing its corrosion resistance compared to simple sterilization in EtOH, while in titanium and its alloys, autoclave and UV-light accelerates its corrosion rate by accelerating the kinetics of oxygen reduction.