The (Ru0.3Ti0.34Sn0.3Sb0.06)O2–TiO2 nanotubes (TNTs) anode has been prepared via anodization, deposition, and annealing. X-ray diffraction, field-emission scanning electron microscopy, cyclic voltammetry, and linear scanning voltammetry were used to scrutinize the electrodes and the electrochemical activity. The results indicate that highly ordered TNTs with large specific surface area could be implanted with active metal oxides. The catalyst firmly binds with the TNTs and enhances the electrochemical stability of the electrode. It displays high over-potential for oxygen evolution reaction. Accordingly, the constructed (Ru0.3Ti0.34Sn0.3Sb0.06)O2–TNTs anode exhibits a greater potential difference (ΔE) between the evolutions of oxygen and chlorine than that exhibited by the traditional dimensionally stable anode, which is beneficial for improving the selectivity toward chlorine evolution reaction. This superior performance is explained in terms of the surface properties and geometric structure of coated catalyst, as well as the electrochemical selectivity ascribed by the addition of tin and antimony species.