The objective of this study was to establish the influence of polyelectrolyte characteristics (molecular weight and charge density) on the properties of oil-in-water emulsions containing oil droplets surrounded by surfactant–polyelectrolyte layers. A surfactant-stabilized emulsion containing small droplets (d₃₂≈0.3 μm) was prepared by homogenizing 20 wt% corn oil with 80 wt% emulsifier solution (20 mM SDS or 2.5 wt% Tween 20, 100 mM acetate buffer, pH 3) using a high-pressure valve homogenizer. This primary emulsion was then diluted with various chitosan solutions to produce secondary emulsions with a range of chitosan concentrations (3 wt% corn oil, 0–1 wt% chitosan). The influence of the molecular characteristics of chitosan on the properties of these emulsions was examined by using chitosan ingredients with different molecular weights (MW  15, 145, and 200 kDa) and degree of deacetylation (DDA  40, 77, and 92%). The electrical charge and particle size of the secondary emulsions were then measured. Extensive droplet aggregation occurred when the chitosan concentration was below the amount required to saturate the droplet surfaces, but stable emulsions could be formed at higher chitosan concentrations. The ζ-potential and mean diameter (d₃₂) of the particles in the secondary emulsions was not strongly influenced by chitosan MW, however the chitosan with the lowest DDA (40%) produced droplets with smaller mean diameters and ζ-potentials than the other two DDA samples examined. Interestingly, we found that stable multilayer emulsions could be formed by mixing medium or high MW chitosan with an emulsion stabilized by a non-ionic surfactant (Tween 20) due to the fact the initial droplets had some negative charge. The information obtained from this study is useful for preparing emulsions stabilized by multilayer interfacial layers.