This study investigated the formation formation mechanism of rice glutelin (RG)-gum arabic (GA) complex using multispectral techniques and molecular simulations. RG-GA-perilla oil (PO) emulsions were constructed, and their microstructure, emulsifying, rheological, stability, and digestion properties were systematically evaluated. Turbidity and ζ-potential showed effective RG-GA complexation at pH 3.5, with GA concentration influencing their electrostatic interactions. Multispectral and molecular docking demonstrated that RG and GA interacted through hydrophobic and hydrogen bonding. RG's secondary structure from an α-helix/random coil to β-sheet/β-turn, establishing ordered conformation. At 1.5 w% GA, RG-GA-PO emulsion exhibited reduced particle size and uniform droplet distribution.The emulsions displayed enhanced emulsifying and rheological properties, along with improved stability against thermal processing, freeze-thaw and oxidation. In vitro digestion studies revealed that 1.5 w% GA contributed to PO stability during gastric digestion by inhibiting RG degradation. The RG-GA complex facilitated PO release in small intestine, with a maximum FAA release rate of 58.06 ± 3.83 %.