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Mesoporous TiO₂ has gained increasing interest because of its outstanding properties and promising applications in a wide range of fields. Herein, we report the facile synthesis of ordered mesoporous black TiO₂ (OMBT) materials, which exhibit excellent photocatalytic hydrogen evolution performances. In this case, the employment of a thermally stable and high-surface-area mesoporous TiO₂ as the hydrogenation precursor is the key for fabricating the OMBT materials, which not only facilitate H₂ gas diffusion into TiO₂ and interaction with their structures but also maintain the ordered mesoporous structures as well as inhibit the phase transformation (from anatase to rutile) and crystal growth during hydrogenation at 500 °C. The resultant OMBT materials possess a relatively high surface area of ∼124 m² g^–1 and a large pore size and pore volume of ∼9.6 nm and 0.24 cm³ g^–1, respectively. More importantly, the …