Harnessing molecular design principles toward functional applications of ion-containing macromolecules relies on diversifying experimental data sets of well-understood materials. Here, we report a simple, tunable framework for preparing styrenic polyelectrolytes, using aqueous reversible addition-fragmentation chain transfer (RAFT) polymerization in a parallel synthesis approach. A series of diblock polycations and polyanions were RAFT chain-extended from poly(ethylene oxide) (PEO) using (vinylbenzyl)trimethylammonium chloride (PEO-b-PVBTMA) and sodium 4-styrenesulfonate (PEO-b-PSS), with varying neutral PEO block lengths, charged styrenic block lengths, and RAFT end-group identity. The materials characterization and kinetics study of chain growth exhibited control of the molar mass distribution for both systems. These block polyelectrolytes were also demonstrated to form polyelectrolyte complex (PEC) driven self-assemblies. We present two simple outcomes of micellization to show the importance of polymer selection from a broadened pool of polyelectrolyte candidates: (i) uniform PEC-core micelles comprising PEO-b-PVBTMA and poly(acrylic acid) and (ii) PEC nanoaggregates comprising PEO-b-PVBTMA and PEO-b-PSS. The materials characteristics of these charged assemblies were investigated with dynamic light scattering, small-angle X-ray scattering, and cryogenic-transmission electron microscopy imaging. This model synthetic platform offers a straightforward path to expand the design space of conventional polyelectrolytes into gram-scale block polymer structures, which can ultimately enable the development of more sophisticated ionic materials into technology.