In this work, the effect of interaction between mesquite gum (GM) and chitosan (Q) on the interfacial properties of adsorbed layer in the water-Canola oil interface, and their influence in the rheological properties, structure and stability of emulsions oil-in-water (O/W) and water-in-oil-in-water (W₁/O/W₂), were studied. The interfacial results showed that there is an associative (electrostatic) interaction between both macromolecules at the pH 3.8, influenced by the biopolymer concentration ratio and oil phase characteristic. The interfacial apparent viscosity and the interfacial creep-compliance properties of adsorbed layer were increases when using 10%GM-0.4%Q. The electrostatic complex (10%GM-0.4%Q) gave the minor coalescence kinetics and their rheological properties exhibited a mayor elastic character with little dependence regarding the aging time of emulsion O/W, and provided greater stability for the multiple system W₁/O/W₂.