The stability, rheological and morphology properties of oil-in-water emulsions coated by ovalbumin (OVA)/gum arabic (GA) complexes were evaluated. At a ratio of 1:2, the emulsions showed better creaming and oxidative stability. Above or below 1:2, the emulsions were unstable due to depletion or bridging flocculation and the rates of lipid oxidation for 30-day storage were significantly higher. All emulsions exhibited elastic gel-like rheological properties. But the apparent viscosity (η) and storage modulus (G′) of emulsions at a ratio of 1:2 were higher than that of 1:1 and 1:3, which attributed to the electrostatic repulsion and ordered spatial structure of emulsions. Meanwhile, the Raman spectral results showed the OVA/GA complexes stabilizing system induced lipid chain disorder or lipid–protein interactions modifications, which may reflect the formation of a gel-like structure in the emulsion.