In this study, we aimed to optimize the extraction of polysaccharides from the leaves of Rhododendron aganniphum and investigate its rheological properties and antioxidant activity. After optimizing the operating parameters using a Box-Behnken design (BBD), the results showed that the optimal ultrasound-assisted extraction conditions were as follows: extraction temperature, 55°C; liquid-solid ratio, 25:1; extraction time, 2.2h; and ultrasound treatment power, 200W. The optimized experimental yield of polysaccharides by ultrasound-assisted extraction (PUAE) was 9.428%, higher than that obtained by hot water extraction (PHWE) for 12h at the same liquid-solid ratio and extraction temperature. In the in vitro antioxidant activity tests, PUAE had higher positive radical scavenging activity for hydroxyl, superoxide and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals than PHWE. However, PUAE and PHWE solutions had similar intermolecular interactions in the steady-shear flow and dynamic viscoelasticity tests, resulting in similar macroscopic behaviour. With respect to the apparent viscosity, storage modulus (G') and loss modulus (G″) of PUAE were lower at the same shear rate or angular frequency. All PUAE solutions exhibited non-Newtonian shear-thinning pseudoplastic behaviour that was accurately described by the Carreau model but was better fit by the power-law model at high shear rates (≥1/s), which demonstrated that the variation in the apparent viscosity dependence was greater at higher concentrations and shear rates. The G' and G″ of the solutions increased as the experimental frequency increased from 0.05 to 500rad/s under all experimental concentrations, and the modulus crossover point decreased gradually with increasing PUAE concentration. The above results demonstrated that the ultrasound-assisted extraction methods gave a higher yield of polysaccharides from the leaves of R. aganniphum with a shorter extraction time than the hot water extraction method, which could affect the apparent viscosity and dynamic viscoelasticity. PUAE presented good radical scavenging activity for DPPH, superoxide and hydroxyl radicals in vitro and could be used as a natural antioxidant in the food and medical industries.