The relationship between the composition and structure of food emulsions was evaluated from the effect of a mixture of emulsifiers Whey protein (WPI) - Tween 80 (T80) and the oil phase features, such as chain length and unsaturation degree (sunflower oil, a long chain triacylglycerol - LCT or NEOBEE® 1053, a medium chain triacylglycerol - MCT). Emulsions with LCT showed higher droplet size than MCT as a consequence of its higher viscosity. All emulsions exhibited shear thinning behavior, but the viscosity was influenced by their interface composition. An occurrence of the destabilization mechanism by creaming was observed in turbidimetric measurements, but no visual phase separation could be observed, indicating a good kinetic stability after a 7-day storage. The initial interfacial tension of the water-LCT or water-MCT oil was about 25 mN/m, but the WPI addition (1% w/w) reduced the initial interfacial tension to approximately 20 mN/m. The increase of T80 concentration led to a decrease of the interfacial tension, reaching a value around 10 mN/m in systems with pure T80. The curves of interfacial tension of systems with LCT or MCT showed differences in the decay rate of tension over time. These differences were attributed to characteristics of the oil phase (hydrophobicity, unsaturation degree, presence of impurities) and the different proportions of each emulsifier within the mixture of emulsifiers. Finally, a higher viscoelastic interface was observed in LCT emulsions, which were mainly stabilized by WPI molecules. Such molecules presented a higher resistance to the displacement due to the competitive adsorption phenomenon, since the LCT is a more hydrophobic oil. On the other hand, the interface with MCT and a higher T80 concentration was less viscoelastic due to an easier displacement of WPI from the interface and the replacement by T80. The results indicate that T80 can be used in combination with WPI to produce emulsions with good stability and lower concentration of synthetic compounds. Lastly, the interfacial layer composition is not only dependent on the WPI-T80 ratio in the bulk phase, but also on the oily phase features. These results provide a potential strategy for designing emulsified foods based on the choice of ingredients and knowledge of the interaction between them.