In order to investigate the effect of linoleic acid (LOA) combined with rice glutenin (RG) on the molecular structure and physicochemical properties of extruded rice starch (ERS), ERS-RG-LOA with 10% RG addition (by mass of RS, hereinafter the same) and different LOA additions (by mass of RS, hereinafter the same) were prepared by a twin-screw extruder, with rice starch (RS), RG and LOA as the raw materials. ternary complexes, the effects of LOA addition on the molecular structure and physicochemical properties of ERS-RG-LOA ternary complexes were investigated based on the characterisation and testing by XRD, FTIR, low-field nuclear magnetic resonance (LF-NMR), DSC, rheometer, fast viscosity analyser, SEM, and laser particle sizer. The results showed that compared with ERS and ERS-RG prepared by adding RG only, the short-range ordered structure of ERS-RG-LOA ternary complexes was significantly increased by the addition of LOA, the relative crystallinity increased, the viscoelasticity, the thermal stability and the binding ability of water molecules were enhanced, the pasting temperature was increased, a denser microstructure was presented, and the peak viscosity was reduced. The relative crystallinity of ERS-RG-LOA ternary complex ERS-RG-1% was 14.54%±0.51%, the degree of short-range order (DO) was 0.971±0.005, the energy storage modulus was significantly higher, and the water-bound (1.77%±0.06%) and weakly-bound (4.39%±0.01%) water contents increased. content increased. The water absorption index (WAI) of the ERS-RG-LOA ternary complex did not change significantly compared to ERS-RG, but the water solubility index (WSI) was significantly lower.