This dissertation delineates my research on the electrostatically driven self-assembly on a wide range of materials. These materials include zeolites where metal cations act as structure directing agents, polyelectrolyte nanoparticle complexes with tunable interparticle separation, stabilized polyelectrolyte complex coacervate microdroplet dispersions and complex coacervate protocells with encapsulated enzymes to model biomolecular condensates. In all these systems, coulombic interactions play a central role in governing the functionality of the resultant material in distinct ways. For zeolites, the valency of the metal cation influences their micropore topology and the co-precipitation of different structures can be accomplished by tuning the cation content. In the case of polyelectrolyte-nanoparticle systems, the charge ratio of these two components directs the average interparticle distance in the complex which can be effectively manipulated. The coacervate microdroplet dispersions were studied in high throughput, and the addition of comb-polyelectrolytes suppress their coalescence and provide long-term stability against high ionic screening. Enzymes spontaneously partition into these coacervate domains due to their heterogenous surface charge, and such stabilized coacervate microdroplets can serve as in vitro protocells models and can elucidate the reaction-diffusion kinetics of enzymatic reactions.