<p>The precise and directed assembly of multi-component aggregates represents a long-standing goal in materials chemistry, with the universal integration of neutral clusters standing as a central challenge in the field. To address this issue, this study introduces for the first time a “cation-mediated co-crystallization” strategy. By controllably functionalizing neutral aluminum molecular rings with cationic moieties, we have successfully overcome the challenge of their electrostatic assembly with polyoxometalates. This approach breaks through the limitations of traditional “ion-pair” assembly regarding precursor charge states, thereby incorporating a wide variety of neutral clusters into the design space for feasible assembly. The strategy demonstrates excellent structural extensibility: the cationic modification sites can be flexibly regulated on either the exterior or interior of the aluminum rings, with potential future extension to diverse polyanionic cluster systems. It is particularly noteworthy that the materials prepared based on this strategy exhibit outstanding solution processability. When incorporated as a dielectric dopant into a polymer matrix, they achieve a remarkable “1 + 1 &gt; 2” synergistic enhancement effect: not only successfully breaking the inherent trade-off between the dielectric constant and dielectric loss in polymers—with the aluminum rings contributing a high capacitance density (∼11.19) and low dielectric loss (∼0.03)—but also provides high breakdown strength (∼740 MV m⁻¹) by the polyoxometalates. This work establishes an innovative paradigm for achieving directed macroscopic functional assembly through precise “encoding” of molecular-level cluster interactions.</p>