Abstract: A bilayer emulsion co-stabilized from zein particles (ZCP) and propylene glycol alginate (PGA) was prepared by layer-by-layer electrostatic deposition (LBL). The effects of different concentrations of PGA, PGA and zein particles on the surface of oil droplets on the apparent properties, physical stability and microstructure of the two-layer emulsion were investigated. The results showed that the droplets were uniform spheres and formed a dense network in the emulsion. The addition of PGA improved the physical stability of the bilayer emulsion. With the increasing of PGA concentration, the particle size of the double emulsion droplets gradually decreased and formed a network structure. The stability of the bilayer emulsion was gradually enhanced, and the PGA had better emulsifying property in terms of the order of addition. When the PGA concentration was increased to 0.05%, the double-layer emulsion first added to the PGA had a smaller droplet size. The novel bilayer emulsion in which the zein granules and the propylene glycol alginate synergistically stabilized had good development potential.