The anodic oxidation kinetics and electrochemical properties of the passive surfaces of Ti, Ni, and Ti‐Ni alloys (0.2–37.5 w/o) in (pH 5.6 and 10.6) solutions with and without redox couples have been investigated by electrochemical methods. Measurements have been made also on single crystals of (n‐type) and (p‐type) with known electrophysical parameters. It was found that the passive surface of pure Ti and Ni electrodes having a thin‐phase oxide film shows specific features of semiconductor electrodes. The electrochemical behavior of passive metal electrodes depends on the potential distribution at the passive metal/solution interface. The rate of anodic oxidation of Ti‐Ni alloys is close to that of pure Ti. The solution ion oxidation reactions are greatly facilitated on the oxidized alloys as compared to Ti. To explain the results obtained a specific model of the alloy oxide layer structure has been adopted.