Soft colloidal particles with multiple surface patches Of differing composition are critical to the development of complex macroscopic structures that can serve as interfacial catalysts, macroscale surfactants, electronically responsive materials, and drug delivery vehicles. Here, we present a continuous process for the scalable formation of soft colloidal particles with multiple surface domains that employs well-established principles of polymer precipitation and phase separation to controllably shape particle architectures. Our results illustrate the broad range of particle morphologies, including Janus and Cerberus structures, and surface compositions accessible to our versatile solution-based assembly system. We also identify polymer diffusion, precipitation, and vitrification as the primary determinants of particle structure for the first time.