There is great interest in the food, cosmetic and pharmaceutical industry in the use of proteins and polysaccharides as natural hydrocolloids to create novel emulsion systems with improved stability and functionality. For example, the electrostatic interaction between proteins and polysaccharides may be used to form oil-in-water (O/W) emulsions with multilayered interfacial membranes around oil droplets or multilayer emulsions. This type of emulsions have been developed using the layer-by-layer (LbL) technique, which consists of direct adsorption of an oppositely charged polyelectrolyte layer (e.g. polysaccharides) on a primary layer of ionic emulsifiers (e.g. proteins). The polymeric structure and electrical charge of proteins make them a special class of compounds very suitable for its utilization in the LbL technique. In recent years, the utilization of proteins as emulsifiers in food and pharmaceutical industry has been turning towards plants as a preferred alternative to animal-based sources. This article reviews the current understanding of the utilization of different vegetable proteins as emulsifier in order to stabilize O/W multilayer emulsion systems. Additionally, it highlights some potential applications of the multilayer emulsion technology in the industry, for improving the stability of emulsions to environmental stresses and for developing controlled or triggered release systems.