We demonstrate an electrochemical approach to prepare a highly active and stable (Zn, Ru)-doped TiO₂ (Ru_0.26Ti_0.73Zn_0.01O_x) for electrochemical generation of KClO₃. The essential ingredients of this approach consists of (1) co-electrodeposition of Ru, Ti and Zn as metallic alloy and then annealing it to oxide (2) dissolution under electrochemically oxidative acidic environment of Ru and Zn-rich surface clusters having high selectivity towards oxygen evolution reaction (OER) leaving Ti-enriched structure that is more selective to chlorine evolution reaction (CER) and (3) using this electrocatalyst for KClO₃ production under near-neutral pH conditions. Dissolution of Ru- and Zn enriched surfaces result in porous structure with higher electrochemical surface area and roughness. Furthermore, this electrochemical dissolution of (Zn, Ru)-rich surface results in electrocatalytic structure that is self-selective towards KClO₃ formation with higher specific activity. The co-electrodeposition of Zn aids (1) the formation of roughened and porous surface structure through surface dissolution of Zn- or ZnO clusters and (2) the enhancement of conductivity of electrocatalyst through formation of oxygen vacancies. The obtained structure has been found to show higher specific activity, activity and stability towards KClO₃ production in comparison to untreated (Zn, Ru)-doped TiO₂ or Ru-doped TiO₂ or RuO₂.