Developing chloroplast-like bio-photo-coupled catalysts is essential for cost-effective and sustainable green manufacturing; however, significant challenges remain due to their compositional complexity. Herein, we establish a novel and versatile biocompatible hydrogen-bonded organic framework (HOF)-based platform for the one-pot construction of integrated artificial photoenzymatic systems. A rationally designed HOF with photosystem I–like architecture and functionality self-assembles from three tectons, in which a light-harvesting monomer 1 and an electron-transferring rhodium single-atom-anchored monomer 2 are precisely organized at the nanoscale through a membrane-protein-complex-like skeleton monomer 3. The resulting all-in-one photocatalytic system achieves up to a 200% enhancement in nicotinamide cofactor (NAD(P)H) regeneration under visible light compared with mixture systems, owing to the enhanced photoinduced electron generation and transfer. Furthermore, two different artificial photosynthesis systems are fabricated via in situ trapping of NAD(P)H-dependent enzymes during HOF crystallization, enabling selective CO2 reduction and nitroaromatic pollutant degradation. Both HOF-based enzyme-photo-coupling systems exhibit efficient bioconversion and recyclability. This work presents a general and modular strategy for integrating photoredox and enzymatic catalysis within supramolecular frameworks, opening new avenues for solar energy utilization and sustainable chemical technologies.