The utilization of liquid-liquid phase separated systems has seen increased attention as synthetic cell platforms due to their innate ability to sequester interesting, functional, and biologically relevant materials. However, their applications are limited by the temporal stability of such condensed phases. While there are a number of strategies toward droplet stabilization, in our group we have developed a polymer-based approach to stabilize complex coacervate microdroplets. These protocells are remarkably robust and have been utilized to support a number of new protocellular applications. Here, we describe in detail the methodologies we have developed for the synthesis of the starting components, their formation into stable, cargo-loaded protocells, and how these protocells are treated post-formation to purify and analyze the resultant functional self-assembled systems.