This study reports the spontaneous formation of core-shell coacervate-based compartments through the evaporation of a sessile droplet on a thin-oil-coated substrate. The droplet, composed of dextran, polyethylene oxide (PEO), lactoferrin, and ovalbumin, undergoes multiple liquid-liquid phase separations (LLPS) driven by evaporation, leading to the formation of hierarchical compartments. These compartments, cell-sized (~10 μm), resemble a protocell encapsulating an intracellular organelle. The formation and maintenance of these compartments are stabilized by stagnation points within the evaporating droplet, which are created by convective capillary flows induced by the maximum evaporation rate at the liquid-liquid-air contact line. The presence of proteins, such as lactoferrin and ovalbumin, further enhances the stability and complexity of these compartments. Additionally, the study demonstrates that RNA molecules can be recruited into these coacervate compartments, highlighting their potential for organizing biochemical reactions. This work provides insights into the spontaneous formation and maintenance of hierarchical compartments under non-equilibrium conditions, offering a simple and robust method to create complex cellular architectures that mimic real-life scenarios.This study reports the spontaneous formation of core-shell coacervate-based compartments through the evaporation of a sessile droplet on a thin-oil-coated substrate. The droplet, composed of dextran, polyethylene oxide (PEO), lactoferrin, and ovalbumin, undergoes multiple liquid-liquid phase separations (LLPS) driven by evaporation, leading to the formation of hierarchical compartments. These compartments, cell-sized (~10 μm), resemble a protocell encapsulating an intracellular organelle. The formation and maintenance of these compartments are stabilized by stagnation points within the evaporating droplet, which are created by convective capillary flows induced by the maximum evaporation rate at the liquid-liquid-air contact line. The presence of proteins, such as lactoferrin and ovalbumin, further enhances the stability and complexity of these compartments. Additionally, the study demonstrates that RNA molecules can be recruited into these coacervate compartments, highlighting their potential for organizing biochemical reactions. This work provides insights into the spontaneous formation and maintenance of hierarchical compartments under non-equilibrium conditions, offering a simple and robust method to create complex cellular architectures that mimic real-life scenarios.