The self-assembly of charged macromolecules forms the basis of all life on earth. From the synthesis and replication of nucleic acids, to the association of DNA to chromatin, to the targeting of RNA to various cellular compartments, to the astonishingly consistent folding of proteins, all life depends on the physics of the organization and dynamics of charged polymers. In this dissertation, I address several of the newest challenges in the assembly of these types of materials. First, I describe the exciting new physics of the complexation between polyzwitterions and polyelectrolytes. These materials open new questions and possibilities within the context of drug packaging and delivery, a selection of which are addressed in the second chapter. In the third chapter, fundamental questions about the chemical characteristics that influence the phase separation of polyzwitterions and polyelectrolytes are explored systematically. Finally, in the fourth chapter, the phenomenon of coacervation is harnessed in the electrochemical context, and several types of measurements of these properties are described in detail. This work represents the current state-of-the-art in the field of charged systems, and future work to create technologies (in the biomedical context, in particular) can all apply the fundamental results illuminated herein.