Bioinspired photosynthetic systems integrating photocatalysts and enzymes offer a promising platform for the conversion of CO₂ into value-added chemicals. However, their practical application is often hindered by catalyst/enzyme deactivation and inefficient electron transfer in multistep photochemical processes. In this study, we report the use of Janus-type DNA nanosheets (NSs), engineered with two distinct DNA sequences on opposite faces, as spatially programmable scaffolds for the selective immobilization of a Rh-based photocatalyst and formate dehydrogenase (FDH). This design enables precise spatial organization of the catalytic components to facilitate efficient CO₂ reduction. Four distinct configurations were constructed: (1) Rh complex immobilized on NS (NS1), (2) FDH immobilized on NS (NS2), (3) Rh complex and FDH immobilized on opposite faces (NS3), and (4) both catalysts co-immobilized on the same face (NS4). The catalytic performance for formate production was found to be strongly dependent on the spatial arrangement of the Rh complex and FDH. Among the systems tested, NS1 coupled with free FDH exhibited the highest activity, followed by NS3, NS2 with free Rh complex, NS4, and the free catalyst/enzyme mixture. The NS1 system, combined with free FDH, achieved a turnover number (TON) of 1,360 for formate production based on NAD⁺ consumption—the highest reported TON for Rh-based photocatalyst/enzyme hybrid systems to date. These findings highlight the critical role of nanoscale spatial compartmentalization in enhancing catalytic efficiency and offer valuable design principles for developing next-generation artificial photosynthetic systems.