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Environmentally friendly catalysts with excellent performance and low cost are critical for photocatalysis. Herein, using hydrogenated TiO 2 (h-TiO 2 ) nanosheets with enriched oxygen vacancies as the support, two-dimensional CoO/h-TiO 2 Z-scheme heterostructures are fabricated for hydrogen production through photocatalytic water splitting. It is revealed that the oxygen vacancies in h-TiO 2 can inhibit the oxidation of Co 2+ into high-valence Co 3+ during the hydrothermal reaction and thermal treatment processes. A CoO/h-TiO 2 Z-scheme heterostructure possesses a space charge region and a built-in electric field at the interface, and oxygen vacancies in h-TiO 2 can provide more reactive sites, which synergistically improve the separation and transportation of photogenerated carriers. As a result, the photocatalytic hydrogen evolution rate achieves 129.75 μmol•h −1 (with 50 mg of photocatalysts) on the optimized CoO/h-TiO 2 heterostructures. This work provides a new design idea for the preparation of excellent TiO 2 -based photocatalysts.