High metal oxidation state results in high oxygen-to-metal coverage. The high oxygen to metal coverage forms a stable protective metal-oxide layer at the surface and protects the bulk of the material from degradation against corrosion attack. Current study uses the theoretical valence electron count (VEC) or electron per atom (e/a) ratio to determine average oxidation states of α-Ti(Au) phase below eutectoid point and Ti3Au intermetallic phase. This was done in order to study the effect of α-Ti(Au) and Ti3Au phases on average oxidation state of binary Ti–Au alloys with various gold (Au) content. Using the theoretically determined oxidation states, it was possible to calculate the average oxidation state of Ti–Au alloys comprised of α-Ti(Au) + Ti3Au phases based on the volume fraction ratio. Oxidation state increased more with an increase in ratio of Ti3Au phase, in direct correlation with the experimentally observed increase in corrosion resistance. However, the mechanistic origin of improved corrosion resistance in Ti–Au alloys remain insufficiently understood. The higher oxidation state of Ti3Au suggests enhanced oxygen affinity and improved stability of the passive oxide film. The framework may be extended to other Ti-based biomedical alloy systems.