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 process involves multiple, coupled segregative and associative liquid-liquid phase separations, which are stabilized by stagnation points within the evaporating droplet. These points are formed by convective capillary flows induced by the maximum evaporation rate at the liquid-liquid-air contact line. The resulting hierarchical compartments resemble a cell encapsulating an intracellular organelle and can sustain themselves without external intervention. The compartments are cell-sized (-10 μm) and maintain their structure despite the risk of fusion. The study also demonstrates the recruitment of RNA into these compartments, showing that they can function as membrane-free, compartmentalized structures. The method involves the spontaneous evaporation of a droplet on an organics-wetted surface, which allows for the creation and maintenance of complex cellular architectures under laboratory conditions that mimic real-life scenarios. The findings provide insights into the spontaneous formation and maintenance of hierarchical compartments under non-equilibrium conditions, offering a glimpse into the real-life scenario of primitive cellular structures. The research highlights the role of convective capillary flows in maintaining the structure of these compartments and the importance of surface properties in controlling droplet behavior. The study also shows that the presence of proteins is crucial for the formation of the core-shell architecture, as they can trigger associative liquid-liquid phase separation. The results demonstrate that the spontaneous evaporation of a sessile droplet can lead to the formation of complex, membrane-free, hierarchical compartments, which can be sustained by flow-assisted mechanisms. The study provides a simple strategy for creating and maintaining complex cellular architectures under laboratory conditions 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 process involves multiple, coupled segregative and associative liquid-liquid phase separations, which are stabilized by stagnation points within the evaporating droplet. These points are formed by convective capillary flows induced by the maximum evaporation rate at the liquid-liquid-air contact line. The resulting hierarchical compartments resemble a cell encapsulating an intracellular organelle and can sustain themselves without external intervention. The compartments are cell-sized (-10 μm) and maintain their structure despite the risk of fusion. The study also demonstrates the recruitment of RNA into these compartments, showing that they can function as membrane-free, compartmentalized structures. The method involves the spontaneous evaporation of a droplet on an organics-wetted surface, which allows for the creation and maintenance of complex cellular architectures under laboratory conditions that mimic real-life scenarios. The findings provide insights into the spontaneous formation and maintenance of hierarchical compartments under non-equilibrium conditions, offering a glimpse into the real-life scenario of primitive cellular structures. The research highlights the role of convective capillary flows in maintaining the structure of these compartments and the importance of surface properties in controlling droplet behavior. The study also shows that the presence of proteins is crucial for the formation of the core-shell architecture, as they can trigger associative liquid-liquid phase separation. The results demonstrate that the spontaneous evaporation of a sessile droplet can lead to the formation of complex, membrane-free, hierarchical compartments, which can be sustained by flow-assisted mechanisms. The study provides a simple strategy for creating and maintaining complex cellular architectures under laboratory conditions that mimic real-life scenarios.