Polyelectrolyte complex (PEC) hydrogels, which self-assemble via complexation of oppositely charged block polymers, have recently risen to prominence owing to their unique characteristics such as hierarchical microstructure, tunable bulk properties, and the ability to precisely assimilate charged cargos (i.e., proteins and nucleic acids). Significant foundational research has delineated the structure-property relationship of PEC hydrogels for use in a wide range of applications. In this Perspective, we summarize key findings on the microstructure and bulk properties of PEC hydrogels and discuss how intrinsic and extrinsic factors can be tuned to create specifically tailored PEC hydrogels with desired properties. We highlight successful applications of PEC hydrogels while offering insight into strategies to overcome their shortcomings and elaborate on emerging opportunities in the field of electrostatic self-assemblies.