A wet‐incipient impregnation method was reported to synthesize hierarchical porous bimetallic (Co, Zn)‐zeolitic imidazolate frameworks (ZIF‐8)/TiO₂ (Co@ZIF‐8/TiO₂) for green hydrogen generation via photocatalytic water splitting. Co@ZIF‐8/TiO₂ showed higher photocatalytic efficiency than TiO₂, with a hydrogen generation rate (HGR) of 13 mmol·h⁻¹·g⁻¹ with a 151‐fold increase in the catalytic performance of TiO₂. The photocatalytic HGR of Co@ZIF‐8/TiO₂ was superior to that of the ZIF‐8/TiO₂ heterostructure. Co@ZIF‐8 showed a hierarchical porous structure containing micropores and mesopores regimes, providing a proficient transport channel for charge transfer. This study presents new prospects for using hierarchical porous metal–organic frameworks (MOFs) as support and promoter in photocatalytic applications of semiconductor such as TiO₂.