AbstractCoacervates formed by liquid‐liquid phase separation play significant roles in a variety of intracellular and extracellular biological processes. Recently, substantial efforts have been invested in creating protocells using coacervates. Microfluidic technology has rapidly gained prominence in this area due to its capability to construct monodisperse and stable coacervate droplets. This review highlights recent advancements in utilizing microfluidic devices to construct coacervate‐core‐vesicle (COV) systems. These COV systems can be employed to realize the sequestration and release of biomolecules as well as to control enzymatic reactions within the coacervate systems in a spatiotemporal manner. Lastly, we delve into the current challenges and opportunities related to the development of functional coacervate systems based on microfluidic technology.