Complex coacervate microdroplets, which are formed via spontaneous liquid-liquid phase separation by mixing two oppositely charged polyelectrolytes in water, have emerged as a new paradigm in the fields of origin of life, membraneless subcellular compartmentalization, bioreactors, and drug delivery. However, how to further improve its stability and enhance its selectivity in one particular coacervate system remains a challenge. By generating a membrane-like layer at the surface of coacervate microdroplets via electrostatic interactions between oppositely charged surfactants and polyelectrolytes, we here achieve tunable permeability and enhanced stability of the coacervates at the same time. Depending on the surfactants used, membrane-like layer-coated coacervate microdroplets exhibit different selectivity over solute sequestration and can promote or inhibit DNA hybridization. Our approach provides a practical tool to engineer functional bioinspired microcompartments with potential applications in the fields of controlled drug release and microreactor technology.