The exceptional biocompatibility of emulsion systems that rely on stabilizing protein–polysaccharide particles presents extensive possibilities for the transportation of bioactive carriers, making them highly promising for various biological applications. The current work aimed to explore the phenomenon of complex coacervation between sesame protein isolate (SPI) and four distinct polysaccharides, namely, Arabic gum (GA), carrageenan (CAR), sodium carboxymethyl cellulose (CMC), and sodium alginate (SA). The study objective was achieved by fabricating emulsions through the blending of these polymers with oil at their maximum turbidity level (φ = 0.6), followed by the measurement of their rheological properties. The turbidity, ζ-potential, and particle size were among the techno-parameters analyzed to assess the emulsion stability. The microstructural characterization of the emulsions was conducted using both transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Furthermore, the functional properties were examined using Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The SPI incorporated with SA, CMC, and CAR reached the maximum turbidity (0.2% w/v) at a ratio of 4:1, corresponding to the pH values of 4.5, 3, or 3.5, respectively. The SPI–GA mixture exhibited the maximum turbidity at a ratio of 10:1 and pH 4.5. Results from the FTIR and XRD analyses provided evidence of complex formation between SPI and the four polysaccharides, with the electrostatic and hydrogen bond interactions facilitating the binding of SPI to these polysaccharides. SPI was bound to the four polysaccharides through electrostatic and hydrogen bond interactions. The SPI–CMC and SPI–SA emulsions were more stable after two weeks of storage.