Sustainable and efficient catalytic oxidation of chlorinated volatile organic compounds (CVOCs) poses an enduring challenge. This bottleneck arises from the limited catalytic activity of redox reactions and chlorine desorption, causing catalyst deactivation and secondary pollution. Herein, our sound strategy involves Ru-loaded facet-engineered {201}-TiO2 with tuned defects, thereby boosting its reactivity. Comprehensive characterizations and DFT calculation manifested that Ru/{201}-TiO2, with abundant oxygen vacancies, Ti3+ defects, and robust metal-support interaction, enabled flexible electron transfer to activate O2 and the dissociation of H2O, thus facilitating the continuous generation of reactive oxygen species (ROS), such as •O2– and hydroxyl species. These ROS effectively enhance chlorine desorption and chlorobenzene deep oxidation. Ru/{201}-TiO2 exhibited superior reactivity for chlorobenzene degradation, with an apparent activation energy (Ea) of 31.0 KJ/mol and 100 % chlorobenzene conversion in a 1000-min stability test, even with H2O introduction. Ru/{201}-TiO2 produced 2.2–3.1 times fewer small-molecule chlorinated byproducts than Ru/{101}-TiO2, with no polychlorinated benzenes detected.