The design of compartmentalized colloids that exhibit biomimetic properties is providing model systems for developing synthetic cell-like entities (protocells). Inspired by the cell walls in plant cells, we developed a method to prepare membranized coacervates as protocell models by coating membraneless liquid-like microdroplets with a protective layer of rigid polysaccharides. Membranization not only endowed colloidal stability and prevented aggregation and coalescence but also facilitated selective biomolecule sequestration and chemical exchange across the membrane. The polysaccharide wall surrounding coacervate protocells acted as a stimuli-responsive structural barrier that enabled enzyme-triggered membrane lysis to initiate internalization and killing of . The membranized coacervates were capable of spatial organization into structured tissue-like protocell assemblages, offering a means to mimic metabolism and cell-to-cell communication. We envision that surface engineering of protocells as developed in this work generates a platform for constructing advanced synthetic cell mimetics and sophisticated cell-like behaviors.