Pickering emulsions are stabilized by solid particles that act as emulsifiers and are irreversibly adsorbed at the oil-water interface. The low solubility of flavonoids in water provides a theoretical basis for their use as stabilizers in Pickering emulsions. In this study, luteolin, a natural flavonoid, was combined with two polysaccharides, i.e., carboxymethyl chitosan and hyaluronic acid, to form composite particles, which were subsequently used as emulsifiers to obtain antioxidant and stable food-grade Pickering emulsions. The results showed that luteolin could effectively increase the emulsification effect of polysaccharides. The prepared emulsions exhibited a uniform droplet size, with an average size of approximately 660.23 nm, and the droplets were well dispersed with a PDI of approximately 0.10. The emulsions were still stable even under changing environmental conditions and could maintain good physical stability after 15 days of storage. The accelerated oxidation results showed that the primary oxidation products (peroxide value, POV) of the emulsions were significantly reduced during the storage process after the addition of luteolin. Hence, adding luteolin enhanced the oxidative stability of the emulsions. Therefore, by synergizing luteolin with hyaluronic acid-carboxymethyl chitosan to give composite particles and applying them as emulsifiers, luteolin was shown to significantly improve the emulsion stability, delay lipid oxidation while acting as an active ingredient. These findings provide a theoretical basis for using flavonoids in stabilizing Pickering emulsions, which is conducive to the efficient utilization of flavonoids.