O/W emulsions (pH value 7.0) stabilized by whey protein isolated was prepared as the primary emulsion at first, and then polysaccharides with different electrical properties, e.g. anionic pectin, neutral guar gum, and cationic chitosan were added to the secondary emulsions structure. The influences of pH value, protein and polysaccharide ratio on the formation of protein-polysaccharide multilayer membranes were investigated. It showed that no electrical reaction between guar gum and emulsion particles could be detected. Chitosan could adsorb to the surface of particles at a pH value 5.0~6.0, however, the formed WPI-chitosan secondary emulsions were unstable. Pectin molecules could absorb to the surface of particles and formed WPI-pectin secondary emulsion at the pH value 3.0~5.0. Stable WPI-pectin secondary emulsion could be formed at pectin concentration 0.2%~0.5%. 