Covalent organic frameworks (COFs)‐based photocatalysts have received growing attention for photocatalytic hydrogen (H₂) production. One of the big challenges in the field is to find ways to promote energy/electron transfer and exciton dissociation. Addressing this challenge, herein, a series of olefin‐linked 2D COFs is fabricated with high crystallinity, porosity, and robustness using a melt polymerization method without adding volatile organic solvents. It is found that regulation of the spatial distances between the acceptor units (triazine and 2, 2'‐bipyridine) of COFs to match the charge carrier diffusion length can dramatically promote the exciton dissociation, hence leading to outstanding photocatalytic H₂ evolution performance. The COF with the appropriate acceptor distance achieves exceptional photocatalytic H₂ evolution with an apparent quantum yield of 56.2% at 475 nm, the second highest value among all COF photocatalysts and 70 times higher than the well‐studied polymer carbon nitride. Various experimental and computation studies are then conducted to in‐depth unveil the mechanism behind the enhanced performance. This study will provide important guidance for the design of highly efficient organic semiconductor photocatalysts.

The urgency of reducing pollution and developing clean energy storage requires efficient photocatalytic hydrogen evolution (PHE) tactics. To improve solar conversion efficiency, it is highly imperative to accelerate the photocarriers separation and transport through materials design. A stable hydrogen evolution photocatalyst based on TpPa-COFs (triformylphloroglucinol phenylenediamine covalent organic frameworks) was developed by a molecular-level design strategy. The study successfully introduced a molecular-scale Ir active site onto the surface of TpPa-COFs via coordination bonds. It verified the structural integrity of TpPa-COFs and the existence of Ir through the basic structural characterizations, such as Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). After the Ir-based coordination compound joining, the absorption edge of TpPa-COF-M1 and TpPa-COF-M2 was extended to 750 nm. The TpPa-COF + M1 exhibited the highest photocatalytic H₂ evolution rate of 662 µmol/h (10 mg catalyst) under visible-light (λ ≥ 420 nm) irradiation. The apparent quantum yield (AQY) of TpPa-COF-M1 is calculated to be 1.9%, 3.8%, 4.8%, 2.8%, 1.8%, and 0.3% at monochromatic wavelengths of 420, 450, 470, 500, 550, and 600 nm, respectively. Our findings confirm that the molecular-level design of photocatalysts can effectively boost performance and reduce cost in photocatalytic reactions and provide an important strategy for designing efficient photocatalysts.