Molecular‐Level Spatial Partitioning Enables Synergistic CO ₂ Capture and Photoreduction in a Titanium‐Oxo Cluster

Photocatalytic CO 2 reduction requires the concerted integration of CO 2 capture, charge separation, and multistep redox conversion, yet these functions are rarely embedded within a single atomically precise molecular scaffold. Here, we report a heterometallic titanium‐oxo cluster, Ti 8 Ni 4 , that achieves molecular‐level spatial partitioning of CO 2 adsorption and reduction sites for synergistic photocatalysis. Ti 8 Ni 4 features a rare terminal Ti═O motif that promotes polarized CO 2 binding, together with site‐differentiated Ni centers that act as reduction‐active sites. As a result, Ti 8 Ni 4 exhibits markedly enhanced photocatalytic CO 2 ‐to‐CO conversion compared with structurally related analogues, affording 2.6 mmol g −1 CO with >97% selectivity. Photophysical studies, in situ x‐ray absorption and photoelectron spectroscopies, infrared analysis, and DFT calculations collectively reveal an intramolecularly cooperative mechanism, in which reduced exciton binding facilitates charge separation, directional electron transfer enriches the Ni centers, and spatially differentiated motifs jointly promote CO 2 adsorption and *COOH formation. This work establishes spatial partitioning in atomically precise clusters as a molecular design principle for integrating capture, activation, and conversion in photocatalysis.