Integrating oxide coatings with narrow‐gap hybrid discharge (HD) can modulate ozone (O3) synthesis. O3 concentration () and energy yield (η) for HD can be enhanced by single‐valent oxides, whereas they are reduced by multivalent oxides. The discharge and oxide characterizations suggest that surface catalytic reactions play a crucial role in the synthesis of O3: single‐valent oxide coatings facilitate O3 production by offering abundant catalytic sites for surface catalytic reactions; surface catalytic reactions on multivalent oxide coatings suppress O3 production because of the dominating O3 decomposition over highly active sites of oxygen vacancies. This study is inspirational for designing and fabricating high‐efficiency O3 generators.