This paper addresses on the electrochemical behaviour of three TiMo alloys exposed to simulated physiological environments. Their stability and corrosion resistance was characterized in order to explore the potential application for the manufacturing of implant materials. Ringer's solution together with an acidic modification of the Ringer's solution (pH 3.1) at room temperature were considered. Both electrochemical methods (namely, potentiodynamic polarization curves and electrochemical impedance spectroscopy, EIS), and spatially resolved scanning electrochemical microscopy (SECM), were used. Additionally, surface characterization was made employing optical microscopy and scanning electron microscopy (SEM). The oxide films formed on the TiMo alloys in neutral and acidic Ringer's solutions effectively protect the metal from dissolution in these environments, and no breakdown of the passive layer occurs in the potential range up to +1.00 V vs. SCE. SEM micrographs of retrieved samples do not show corrosion pits, cracks, or any other defects despite the rather high positive potential values reached during the potential excursion. EIS data reveal that two-layer oxide films are formed, consisting of a porous outer layer and a compact inner layer (approximately 5–6 nm thick), the latter accounting almost completely for the corrosion resistance of the materials. The corrosion resistance of the inner compact film towards metal dissolution is smaller in the acidic environment, whereas it increases with higher Mo contents in the alloy. The passive oxide films exhibit dielectric characteristics towards charge transfer when they are imaged by scanning electrochemical microscopy.